Sugar ester peracid on site generator and formulator

ABSTRACT

Methods and systems for on-site generation of peracid chemistry, namely peroxycarboxylic acids and peroxycarboxylic acid forming compositions, are disclosed. In particular, an adjustable biocide formulator or generator system is designed for on-site generation of peroxycarboxylic acids and peroxycarboxylic acid forming compositions from sugar esters. Methods of using the in situ generated peroxycarboxylic acids and peroxycarboxylic acid forming compositions are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. Ser. No.14/878,268 filed Oct. 8, 2015, now U.S. Pat. No. 9,505,715 issued Nov.29, 2016, which is a continuation application of U.S. Ser. No.14/512,530 filed Oct. 13, 2014, now U.S. Pat. No. 9,192,909 issued Nov.24, 2015, which is a continuation application of U.S. Ser. No.13/330,915 filed Dec. 20, 2011, now U.S. Pat. No. 8,889,900 issued Nov.18, 2014, which claims priority to provisional application of U.S. Ser.No. 61/427,951 filed Dec. 29, 2010, which are hereby incorporated byreference in their entireties.

FIELD OF THE INVENTION

The invention relates to methods and apparatus for on-site generation ofperacids, namely peroxycarboxylic acids and peroxycarboxylic acidforming compositions for use as oxidizing agents. In particular, anadjustable biocide formulator or generator system is designed foron-site generation of peroxycarboxylic acids and peroxycarboxylic acidforming compositions from at least one sugar ester. Methods of using thein situ generated peroxycarboxylic acids and peroxycarboxylic acidforming compositions are also disclosed.

BACKGROUND OF THE INVENTION

Peracids, also known as peroxyacids, are known for use as sanitizers,disinfectants, deodorizers, and bleaching agents, among other uses.Peroxycarboxylic acids in particular are known for use as antimicrobialsand bleaching agents. Peracids such as peroxycarboxylic acid have knownchemical disadvantages, namely, they are relatively instable in solutionand decompose to ordinary oxyacids and oxygen.

Conventional peroxycarboxylic acid compositions are made through an acidcatalyzed equilibrium reaction. Most often, the peroxycarboxylic acidsare generated in a chemical plant, and then shipped to customers foron-site use. Due to the limited storage stability of peroxycarboxylicacids they are often packed in special containers and shipped under thestrict Department of Transportation (DOT) guidelines. Certainimprovements to peroxycarboxylic acid stability have proved advantageousfor shipping purposes, as described in U.S. patent application Ser. No.11/847,604, entitled “Shelf Stable, Reduced Corrosion, Ready to UsePeroxycarboxylic Acid Antimicrobial Compositions,” the entire contentsof which are hereby expressly incorporated herein by reference.

Most commercially available products in an equilibrium mixture containexcess hydrogen peroxide in the presence of stabilizers and acidcatalysts, to stabilize and improve the composition's shelf life.Despite stability improvements, excess amounts of reagents (e.g., acids,oxidizing agents, and stabilizers) must be present in the compositionsduring shipping to prevent decomposition. Peroxycarboxylic acidinstability, specifically limited storage stability, is described indetail in U.S. Pat. No. 8,034,759, the entire contents of which arehereby expressly incorporated herein by reference.

Accordingly, it is an objective of the claimed invention to developmethods and systems for on-site generation of peracids, includingperoxycarboxylic acid generating compositions and peroxycarboxylicacids.

A further object of the invention is to develop a system for generationof individual or mixed peracid chemistries according to user- orsystem-specific needs.

A further object of the invention is to develop methods and systems foron-site generation of peracid chemistries to enhance efficacyperformance, reduce transportation cost and hazards, reduce or eliminatewastes and enhance shelf-life of generated peracid chemistries.

BRIEF SUMMARY OF THE INVENTION

An advantage of the invention is a system for on-site generation of abiocide or antimicrobial agent. The system may be formulated into anumber of designs, including for example, a mobile cart or generatorthat is particularly suitable for the on-site generation of peracidchemistries required in batch formulations. It is a particular advantageof the present invention that individual and/or mixed peracidchemistries, including peroxycarboxylic acid forming compositions orperoxycarboxylic acids are generated on-site according to particularneeds of a user or system to provide desired performance againstparticular organisms, as well as providing desired volumes of the samechemistry. These benefits of the present invention effectively eliminatethe need for shipping and/or long-term stability of the productrequiring the addition of various stabilizing agents thereby increasingthe shipping, cost and formulation burdens.

In an embodiment, the present invention is an adjustable biocideformulator or generator system for on-site peroxycarboxylic acid formingcomposition generation including an apparatus with at least one reactionvessel, a series of feed pumps, and an outlet for dosing aperoxycarboxylic acid forming composition. In an embodiment the feedpumps are in fluid connection with the reaction vessel and supplyreagents to produce the peroxycarboxylic acid forming composition andthe reagents may include an ester of a polyhydric alcohol and a C1 toC18 carboxylic acid, a source of alkalinity an oxidizing agent and otherreagents according to the invention. In an embodiment the reactionvessel is in fluid connection with the outlet to dispense theperoxycarboxylic acid forming composition, which may be an individual ormixed peroxycarboxylic acid forming composition as selected by a user-or system-inputted selection.

In a further embodiment, the present invention is a method for on-siteperoxycarboxylic acid forming composition or peroxycarboxylic acidgeneration and may include the steps of inputting a user- orsystem-controlled peroxycarboxylic acid forming composition orperoxycarboxylic acid formulation into a control software for anadjustable biocide formulator or generator system, and mixing one ormore sugar esters of a polyhydric alcohol and a C1 to C18 carboxylicacid, a source of alkalinity and an oxidizing agent at alkaline pH in anadjustable biocide formulator or generator system. In an embodiment theinput formulation selects an individual or mixed peroxycarboxylic acidforming composition or peroxycarboxylic acid and corresponding volume ormass for onsite generation.

The methods of the invention further include the steps of diluting asource of alkalinity to a target concentration. The methods furtherinclude the steps of adding the ester(s) downstream (e.g. after theaddition of the diluted alkalinity source solution).

In a further embodiment, the present invention is a method of cleaningusing an on-site generated peroxycarboxylic acid forming composition andmay include obtaining a user- or system-inputted peroxycarboxylic acidforming composition on-site using an adjustable biocide formulator orgenerator system and applying the peroxycarboxylic acid formingcomposition in an amount sufficient to sanitize, bleach or disinfect asurface in need thereof.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the invention. Accordingly, the drawings anddetailed description are to be regarded as illustrative in nature andnot restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a schematic diagram of a user or controller operatedadjustable biocide formulator apparatus according to the invention.

FIG. 2 shows a diagram of an embodiment of an adjustable biocideformulator apparatus according to the invention using a single reactionvessel.

FIG. 3 shows a diagram of an alternative adjustable biocide formulatorapparatus according to an embodiment of the invention using multiplereaction vessels.

FIG. 4 shows a diagram of a multiple reaction vessel embodiment for theadjustable biocide formulator apparatus according to an embodiment ofthe invention.

FIG. 5 shows a diagram of an embodiment of an adjustable biocideformulator apparatus according to the invention wherein a controller isincluded as a feature of the apparatus.

FIG. 6A shows a diagram of an embodiment of an adjustable biocideformulator apparatus according to the invention, including descriptionof the dosing of raw starting materials (e.g. reagents) for thegeneration of peracid chemistries according to the invention.

FIG. 6B shows a diagram of an embodiment of an adjustable biocideformulator apparatus according to the invention, including descriptionof the dosing of raw starting materials (e.g. reagents) for thegeneration of peracid chemistries according to the invention.

Various embodiments of the present invention will be described in detailwith reference to the drawings, wherein like reference numeralsrepresent like parts throughout the several views. Reference to variousembodiments does not limit the scope of the invention. Figuresrepresented herein are not limitations to the various embodimentsaccording to the invention and are presented for exemplary illustrationof the invention.

DETAILED DESCRIPTION OF THE INVENTION

The present disclosure relates to adjustable biocide formulator orgenerator systems for on-site peracid generation, including for exampleperoxycarboxylic acid forming compositions or peroxycarboxylic acids, aswell as methods of making and using such compositions. The compositionsand systems for making the compositions disclosed herein have manyadvantages over conventional systems and methods for makingperoxycarboxylic acids or peroxycarboxylic acid forming compositions.For example, the systems allow on-site, user- or system-controlledformulation, eliminating the step of shipping hazardous peroxycarboxylicacid compositions to an end user. In addition, there are variousadvantages of the compositions, including having significantly lowerlevels of reactant residues compared to peroxycarboxylic acidcompositions generated using equilibrium reactions, increased stabilityand ability to be generated in situ and/or on site.

The embodiments of this invention are not limited to particular methodsand systems for on-site generation of sugar ester peracids for use asbiocides, which can vary and are understood by skilled artisans. It isfurther to be understood that all terminology used herein is for thepurpose of describing particular embodiments only, and is not intendedto be limiting in any manner or scope. For example, as used in thisspecification and the appended claims, the singular forms “a,” “an” and“the” can include plural referents unless the content clearly indicatesotherwise. Further, all units, prefixes, and symbols may be denoted inits SI accepted form. Numeric ranges recited within the specificationare inclusive of the numbers defining the range and include each integerwithin the defined range.

So that the present invention may be more readily understood, certainterms are first defined. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe invention pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used in the practice of theembodiments of the present invention without undue experimentation, thepreferred materials and methods are described herein. In describing andclaiming the embodiments of the present invention, the followingterminology will be used in accordance with the definitions set outbelow.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

As used herein, “agricultural” or “veterinary” objects or surfacesinclude animal feeds, animal watering stations and enclosures, animalquarters, animal veterinarian clinics (e.g. surgical or treatmentareas), animal surgical areas, and the like.

As used herein, the phrase “air streams” includes food anti-spoilage aircirculation systems. Air streams also include air streams typicallyencountered in hospital, surgical, infirmity, birthing, mortuary, andclinical diagnosis rooms.

The term “cleaning,” as used herein, means to perform or aid in soilremoval, bleaching, microbial population reduction, or combinationthereof.

As used herein, the term “disinfectant” refers to an agent that killsall vegetative cells including most recognized pathogenicmicroorganisms, using the procedure described in A.O.A.C. Use DilutionMethods, Official Methods of Analysis of the Association of OfficialAnalytical Chemists, paragraph 955.14 and applicable sections, 15thEdition, 1990 (EPA Guideline 91-2). As used herein, the term “high leveldisinfection” or “high level disinfectant” refers to a compound orcomposition that kills substantially all organisms, except high levelsof bacterial spores, and is effected with a chemical germicide clearedfor marketing as a sterilant by the Food and Drug Administration. Asused herein, the term “intermediate-level disinfection” or “intermediatelevel disinfectant” refers to a compound or composition that killsmycobacteria, most viruses, and bacteria with a chemical germicideregistered as a tuberculocide by the Environmental Protection Agency(EPA). As used herein, the term “low-level disinfection” or “low leveldisinfectant” refers to a compound or composition that kills someviruses and bacteria with a chemical germicide registered as a hospitaldisinfectant by the EPA.

As used herein, the phrase “food processing surface” refers to a surfaceof a tool, a machine, equipment, a structure, a building, or the likethat is employed as part of a food processing, preparation, or storageactivity. Examples of food processing surfaces include surfaces of foodprocessing or preparation equipment (e.g., slicing, canning, ortransport equipment, including flumes), of food processing wares (e.g.,utensils, dishware, wash ware, and bar glasses), and of floors, walls,or fixtures of structures in which food processing occurs. Foodprocessing surfaces are found and employed in food anti-spoilage aircirculation systems, aseptic packaging sanitizing, food refrigerationand cooler cleaners and sanitizers, ware washing sanitizing, blanchercleaning and sanitizing, food packaging materials, cutting boardadditives, third-sink sanitizing, beverage chillers and warmers, meatchilling or scalding waters, autodish sanitizers, sanitizing gels,cooling towers, food processing antimicrobial garment sprays, andnon-to-low-aqueous food preparation lubricants, oils, and rinseadditives.

As used herein, the phrase “food product” includes any food substancethat might require treatment with an antimicrobial agent or compositionand that is edible with or without further preparation. Food productsinclude meat (e.g., red meat and pork), seafood, poultry, produce (e.g.,fruits and vegetables), eggs, living eggs, egg products, ready to eatfood, wheat, seeds, roots, tubers, leafs, stems, corns, flowers,sprouts, seasonings, or a combination thereof. The term “produce” refersto food products such as fruits and vegetables and plants orplant-derived materials that are typically sold uncooked and, often,unpackaged, and that can sometimes be eaten raw.

As used herein, the term “fouling” shall be understood to mean theundesirable presence of or any deposition of any organic or inorganicmaterial in the applicable composition or chemistry.

As used herein, the term “free” or “substantially free” refers to acomposition, mixture, or ingredient that does not contain a particularcompound or to which a particular compound or a particularcompound-containing compound has not been added. Should the particularcompound be present through contamination and/or use in a minimal amountof a composition, mixture, or ingredients, the amount of the compoundshall be less than about 3 wt-%. More preferably, the amount of thecompound is less than 2 wt-%, less than 1 wt-%, and most preferably theamount of the compound is less than 0.5 wt-%.

As used herein, the phrase “health care surface” refers to a surface ofan instrument, a device, a cart, a cage, furniture, a structure, abuilding, or the like that is employed as part of a health careactivity. Examples of health care surfaces include surfaces of medicalor dental instruments, of medical or dental devices, of electronicapparatus employed for monitoring patient health, and of floors, walls,or fixtures of structures in which health care occurs. Health caresurfaces are found in hospital, surgical, infirmity, birthing, mortuary,and clinical diagnosis rooms. These surfaces can be those typified as“hard surfaces” (such as walls, floors, bed-pans, etc.), or fabricsurfaces, e.g., knit, woven, and non-woven surfaces (such as surgicalgarments, draperies, bed linens, bandages, etc.), or patient-careequipment (such as respirators, diagnostic equipment, shunts, bodyscopes, wheel chairs, beds, etc.), or surgical and diagnostic equipment.Health care surfaces include articles and surfaces employed in animalhealth care.

As used herein, the term “instrument” refers to the various medical ordental instruments or devices that can benefit from cleaning with acomposition according to the present invention. As used herein, thephrases “medical instrument,” “dental instrument,” “medical device,”“dental device,” “medical equipment,” or “dental equipment” refer toinstruments, devices, tools, appliances, apparatus, and equipment usedin medicine or dentistry. Such instruments, devices, and equipment canbe cold sterilized, soaked or washed and then heat sterilized, orotherwise benefit from cleaning in a composition of the presentinvention. These various instruments, devices and equipment include, butare not limited to: diagnostic instruments, trays, pans, holders, racks,forceps, scissors, shears, saws (e.g. bone saws and their blades),hemostats, knives, chisels, rongeurs, files, nippers, drills, drillbits, rasps, burrs, spreaders, breakers, elevators, clamps, needleholders, carriers, clips, hooks, gouges, curettes, retractors,straightener, punches, extractors, scoops, keratomes, spatulas,expressors, trocars, dilators, cages, glassware, tubing, catheters,cannulas, plugs, stents, scopes (e.g., endoscopes, stethoscopes, andarthoscopes) and related equipment, and the like, or combinationsthereof.

As used herein, the term “microorganism” refers to any noncellular orunicellular (including colonial) organism. Microorganisms include allprokaryotes. Microorganisms include bacteria (including cyanobacteria),spores, lichens, fungi, protozoa, virinos, viroids, viruses, phages, andsome algae. As used herein, the term “microbe” is synonymous withmicroorganism.

As used herein, the terms “mixed” or “mixture” when used relating to“peracids,” “peroxycarboxylic acid composition” or “peroxycarboxylicacids” refer to a composition or mixture including more than oneperoxycarboxylic acid, such as a composition or mixture includingperoxyacetic acid (POAA) and peroxyoctanoic acid (POOA).

As used herein, the terms “mixed,” “mixture” or “more than one” whenused relating to esters suitable for use in forming the compositions ofthe invention refer to a composition or mixture including more than oneester group undergoing a perhydrolysis reaction to form theperoxycarboxylic composition. The use of at least one ester of apolyhydric alcohol and a C1 to C18 carboxylic acid according to theinvention includes the use of various forms of the ester, such as themono, di, tri and/or mixtures thereof formations of the particularester. Accordingly, examples of suitable forms of esters for use as“mixtures” or comprising “more than one” include, but are not limitedto, glycerol monooctanoate, glycerol dioctanoate, glycerol trioctanoate,sorbitan monooctanoate, sorbitan dioctanoate, sorbitan trioctanoate, andmixtures and derivatives thereof. Further, as one skilled in the artshall ascertain based upon the description of the invention disclosedherein, the use of an ester source, such as glycerol octanoate, mayfurther comprise the use of the mono, di and tri esters and/or mixturesthereof. According to various embodiments of the invention, the use of“an” ester, such as octanoic glyceride, may include the use of a“mixture” of esters wherein more than one formation of the ester ispresent, including for example the mono, di and tri formations and/ormixtures thereof.

As used herein, the phrases “objectionable odor,” “offensive odor,” or“malodor,” refer to a sharp, pungent, or acrid odor or atmosphericenvironment from which a typical person withdraws if they are able to.Hedonic tone provides a measure of the degree to which an odor ispleasant or unpleasant. An “objectionable odor,” “offensive odor,” or“malodor” has an hedonic tone rating it as unpleasant as or moreunpleasant than a solution of 5 wt-% acetic acid, propionic acid,butyric acid, or mixtures thereof.

As used herein, the terms “peracid” or “peroxy acid” refer to an acidhaving the hydrogen of the hydroxyl group replaced by a hydroxy group.Oxidizing peracids are referred to herein as peroxycarboxylic acids.

As used herein, the term “polyhydric alcohol” or “polyol,” refers to analcohol that has two or more hydroxyl groups. Polyhydric alcoholssuitable for use in the compositions include, but are not limited to,sugars, sugar alcohols, and mixtures and derivatives thereof.

As used herein, the term “sanitizer” refers to an agent that reduces thenumber of bacterial contaminants to safe levels as judged by publichealth requirements. In an embodiment, sanitizers for use in thisinvention will provide at least a 99.999% reduction (5-log orderreduction). These reductions can be evaluated using a procedure set outin Germicidal and Detergent Sanitizing Action of Disinfectants, OfficialMethods of Analysis of the Association of Official Analytical Chemists,paragraph 960.09 and applicable sections, 15th Edition, 1990 (EPAGuideline 91-2). According to this reference a sanitizer should providea 99.999% reduction (5-log order reduction) within 30 seconds at roomtemperature, 25+/−2° C., against several test organisms.

For the purpose of this patent application, successful microbialreduction is achieved when the microbial populations are reduced by atleast about 50%, or by significantly more than is achieved by a washwith water. Larger reductions in microbial population provide greaterlevels of protection.

Differentiation of antimicrobial “-cidal” or “-static” activity, thedefinitions which describe the degree of efficacy, and the officiallaboratory protocols for measuring this efficacy are considerations forunderstanding the relevance of antimicrobial agents and compositions.Antimicrobial compositions can affect two kinds of microbial celldamage. The first is a lethal, irreversible action resulting in completemicrobial cell destruction or incapacitation. The second type of celldamage is reversible, such that if the organism is rendered free of theagent, it can again multiply. The former is termed microbiocidal and thelater, microbistatic. A sanitizer and a disinfectant are, by definition,agents which provide antimicrobial or microbiocidal activity. Incontrast, a preservative is generally described as an inhibitor ormicrobistatic composition.

As used herein the term “sugar” refers to carbohydrates including one,two, or more saccharose groups. Sugars are a group of organic compoundsrelated by molecular structure that comprise simpler members of thegeneral class of carbohydrates. Each sugar consists of a chain of 2 to 7carbon atoms (usually 5 or 6). Sugars have the general formulaC_(n)H_(2n)O_(n), wherein n is between 2 and 7. One of the carbonscarries aldehydic or ketonic oxygen which may be combined in acetal orketal forms and the remaining carbon atoms usually bear hydrogen atomsand hydroxyl groups. In general, sugars are more or less sweet, watersoluble, colorless, odorless, optically active substances which losewater, caramelize and char when heated. Exemplary sugars include, butare not limited to, glucose, sucrose, lactose and mixtures thereof.

As used herein, the term “sugar alcohol” refers to the hydrogenated formof a carbohydrate, wherein the carbonyl group of the carbohydrate hasbeen reduced to a primary or secondary hydroxyl group. Sugar alcoholshave the general formula CH₂OH(CHOH)_(n)CH₂OH, wherein n is from 2 to 5.Exemplary sugar alcohols include, but are not limited to, glycol,ethylene glycol, propylene glycol, glycerol, erythritol,pentaerythritol, threitol, arabitol, xylitol, ribitol, mannitol,sorbitol, sorbitan, dulcitol, iditol, inositol, isomalt, maltitol,lactitol, polyglycitol, 1,4-cyclohexane diol, and mixtures andderivatives thereof. In some embodiments, the sugar alcohol is selectedfrom ethylene glycol, propylene glycol, glycerol, polyglycerol,sorbitol, sorbitan, and mixtures and derivatives thereof.

As used herein, the term “ware” refers to items such as eating andcooking utensils, dishes, and other hard surfaces such as showers,sinks, toilets, bathtubs, countertops, windows, mirrors, transportationvehicles, and floors. As used herein, the term “warewashing” refers towashing, cleaning, or rinsing ware. Ware also refers to items made ofplastic. Types of plastics that can be cleaned with the compositionsaccording to the invention include but are not limited to, those thatinclude polycarbonate polymers (PC), acrilonitrile-butadiene-styrenepolymers (ABS), and polysulfone polymers (PS). Another exemplary plasticthat can be cleaned using the compounds and compositions of theinvention include polyethylene terephthalate (PET).

As used herein, the term “waters” includes food process or transportwaters. Food process or transport waters include produce transportwaters (e.g., as found in flumes, pipe transports, cutters, slicers,blanchers, retort systems, washers, and the like), belt sprays for foodtransport lines, boot and hand-wash dip-pans, third-sink rinse waters,and the like. Waters also include domestic and recreational waters suchas pools, spas, recreational flumes and water slides, fountains, and thelike.

The term “weight percent,” “wt-%,” “percent by weight,” “% by weight,”and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

Embodiments of the Invention

According to an embodiment of the invention methods and apparatus foron-site generation of peracid chemistries for use as cleaning agents,including for example, antimicrobial applications, bleachingapplications, and other cleaning and anti-scaling applications. Themethods and apparatus according to the invention are capable of on-sitegeneration of both individual or mixed peracid chemistries formulatedaccording to user-specifications. The invention overcomes the shortfallsof commercially-available peracids by providing user-specificformulations with enhanced performance efficacy through anon-equilibrium methods of making. In addition, the methods andapparatus use sugar esters as backbone ingredients to generate on-siteperacid chemistries, beneficially reducing the costs and hazardsassociated with transporting active chemistries, providing activechemistries with increased shelf-lives and reduction of waste of activechemistries as a result of on-site user-identified peracid productionaccording to the invention.

The methods and apparatus of the present invention overcome significantlimitations of conventional methods of peracid (i.e. peroxycarboxylicacid) generation, typically acid catalyzed equilibrium reactions. Themethods and apparatus of the present invention overcome the manydownsides to such conventional methods, including, but not limited toelimination of the use of excess amounts of reactants, and hazardousshipping conditions.

While an understanding of the mechanism is not necessary to practice thepresent invention and while the present invention is not limited to anyparticular mechanism of action, it is contemplated that, in someembodiments the benefits afforded according to the invention result fromthe production of a non-equilibrium chemistry using the methods andapparatus of the present invention. Beneficially, the reacted peracidsaccording to the invention are obtained in greater amounts than inequilibrium chemistry wherein greater amounts of unreacted hydrogenperoxide and other reagents would be present. According to the presentinvention, an aqueous solution of the peroxycarboxylic acid(s) producedcontains a relatively higher concentration of peroxycarboxylic acid(s)compared to unreacted hydrogen peroxide component. This is significantlyadvantageous for the anti-microbial and other cleaning applicationsdisclosed herein as desirable according to the embodiments of theinvention.

Rather than providing a peracid composition in an equilibrium mixture,in situ generation of the peracid composition allows the peracids to beproduced stoichiometrically through selecting the composition of thestarting materials. The in situ systems according to the inventiontherefore generate higher concentrations of the peroxycarboxylic acid(s)than are available in equilibrium systems. In particular, according tothe invention the systems generate higher concentrations of theperoxycarboxylic acid(s) and lower concentrations of hydrogen peroxide(e.g. unreacted reagents) than achieved in equilibrium systems. Inaddition, the methods of the present invention generate peroxycarboxylicacid(s) under alkaline conditions and thereafter adjust to acidicconditions to stabilize the peroxycarboxylic acid(s) and ensure theperoxycarboxylic acid(s) compositions do not disassociate.

System for Making On-Site Peracid Compositions

In some aspects, the present invention relates to an adjustable biocideformulator or generator (ABF) apparatus or system for on-site generationof peracid chemistries. As used herein, the terms ABF, ABFsystem/apparatus/generator and the like refer equally to the variousembodiments of the invention disclosing the adjustable biocideformulator, apparatus and/or system disclosed herein according to thevarious embodiments. The ABF system produces peroxycarboxylic acidforming compositions according to the disclosure presented herein.Peroxycarboxylic acid forming compositions refer to the generation ofperoxycarboxylic acids in situ, in a non-equilibrium reaction. Inparticular embodiments of the invention, the system produces the anioncapable of forming peroxycarboxylic acid upon acidification. Accordingto additional aspects of the invention, the ABF system may produceperoxycarboxylic acids.

In some aspects, the system for on-site generation of peroxycarboxylicacid forming compositions may comprise, consist of and/or consistessentially of an apparatus including at least one reaction vessel, aseries of feed pumps and an outlet for dosing the generated chemistryfrom the reaction vessel. In some aspects, the reaction vessels, seriesof feed pumps and the outlet are in fluid connection to provide thereagents used to generate the peroxycarboxylic acid forming compositionin the reaction vessel. In some aspects, the system may also include oneor more reservoirs in fluid connection with the reaction vessels toallow further mixing and/or storage of the peroxycarboxylic acid formingcompositions. In some aspects, the system may optionally comprise atleast one measurement device and/or at least one mechanism suitable formixing the reagents in the reaction vessel(s).

In some aspects of the invention, the reaction vessel meets thehydraulic requirements of the peracid reaction kinetics. Although notintending to be limited by a particular theory of the invention, thekinetics of the perhydrolysis reaction according to the invention arepH, concentration and/or temperature dependent, and the reaction canreach the maximum yield in the order of minutes. The reaction vessel maybe designed in a variety of ways, including for example shape, size,temperature, fluid dynamics (e.g. recirculating or other means ofmodifying the hydraulics of the system) and material.

According to an embodiment of the invention, the reaction vessel mayhave a convex shape at the bottom to assist in drainage of its contentsand assist with mixing of the contents. In addition, the reactionvessels and the system may also employ mixers, such as an impeller, orthe like as one skilled in the art will appreciate, for circulationwithin the reaction vessel, circulation pumps or be gravity-driven,employ additional holding vessels, reagent delivery sensors (e.g. proofof reagent and/or peracid chemistry delivery sensor) or combinations ofthe same to meet the peracid reaction kinetics of the system.

In some aspects of the invention, the system for on-site generation ofperoxycarboxylic acid forming compositions may include at least onemeasurement device or a plurality of measurement devices. Suchmeasurement devices are those suitable to measure one or more reactionkinetics or system operations for the generation of peroxycarboxylicacid forming compositions, including for example devices to measurefluorescence, weight, flow (e.g. flow meters or switches), capacitivelevel, pH, oxidation reduction potential, pressure, temperature andcombinations thereof. Such measurement devices may measure the system'sfeed pumps, reaction vessels, reservoir, outlets, etc.

Examples of additional suitable measurement devices include capacitivelevel sensors, out of product alarms, POA/peroxide monitors, oxychecks,IR/UV/VIS spectroscopy and pressure switches. Still further examples ofsuitable measurement devices are disclosed herein, in addition variousembodiments of those disclosed in U.S. patent application Ser. No.12/108,202, and U.S. Pat. No. 7,547,421, both entitled Apparatus andMethod for Making Peroxycarboxylic Acid, which are herein incorporatedby reference in their entirety.

In some embodiments of the invention, the system provides an acid sourcefor the acidification step to take place in the ABF system. The acidsource may be an acid or an aqueous acid solution. As a result theperoxycarboxylic acid forming composition is acidified toperoxycarboxylic acid within the system. In an embodiment of theinvention, the system may include a feed pump to provide an acid oracidic aqueous solution in fluid communication with one or more reactionvessels or reservoirs. The addition of the acid or acidic aqueoussolution may dilute the peroxycarboxylic acid forming composition toform a peroxycarboxylic acid having a pH of about 1.0 to about 8.0. As aresult, a stabilized formulation is generated by the system. Accordingto certain embodiments, the addition of the acid or acidic aqueoussolution produces peracid formulations with increased stability.However, as one skilled in the art will appreciate, some reactionintermediates are stable for longer periods of time and do not need tobe quenched with acid immediately. For example, some reactionintermediates are stable for at least 24 hours and can be pumped to asump reservoir for dosing into a cleaning process or dosed directly froma reaction vessel. Other peroxycarboxylic acid forming compositions areless stable and the perhydrolysis reaction requires quenching with theacid or acidic aqueous solution to lower the pH and stabilize morepromptly.

According to alternative embodiments of the invention, the ABF systemgenerates peroxycarboxylic acid forming compositions which are acidifiedoutside of the system (i.e., post generator within a customer'sprocess). For example, post-generator acidification may include a cleanin place (CIP) process where the peroxycarboxylic acid formingcomposition (anion solution) is pumped to a temporary holding tank foruse in a CIP system, or pumped directly to a CIP system where the acidis added either in a pipe or the CIP vessel itself. A further example ofpost-generator acidification may include a healthcare application orcertain laundry applications where the acid is added to provide aperoxycarboxylic acid (with an acid pH) to provide bleaching and/orsanitizing benefits of the peracid.

According to additional embodiments of the invention, there are variousapplications for the compositions of the invention where acidificationis not required and/or desired as the use of the peroxycarboxylic acidforming composition (anion solution) is preferred. For example, in alaundry application the acid is not be added in order to benefit fromthe alkaline pH of the anion for bleaching purposes. The alkaline pH forbleaching is obtained from the anion species, as a result theperoxycarboxylic acid forming composition is not quenched with acid.

In some aspects of the invention, the system may include a variety ofsafety mechanisms. Exemplary on-site safety feedback mechanisms for asystem are disclosed in further detail in U.S. Patent Publication No.2009/0208365, which is hereby expressly incorporated by referenceincluding, without limitation, the specification, claims, and abstract,as well as any figures, tables, or drawings thereof. Various safetymechanisms can measure pressure, temperature, difference in pressure,difference in temperature, or a combination thereof and provide aperceptible signal if one or more of these increases above apredetermined level. The level of pressure, temperature, difference inpressure, difference in temperature, or a combination thereof at whichsafety system provides a perceptible signal can be selected to allowintervention to avoid undesirable or unsafe conditions.

In another aspect of the invention, the system may include a coolingsystem on the reaction vessels. A cool system may be in combination witha safety mechanism and/or a measurement device of the system. It may bedesirable to have reaction vessels and/or other components of the systemunder temperature controls. As one skilled in the art will appreciate,exothermic reactions may degrade the reagents according to thegeneration of the peracid compositions of the invention. In addition,there are various safety considerations for a system to avoid increasesin temperature, for example system temperatures in excess of 110° C. Inaddition, according to an embodiment of the invention, the system has atleast one mechanism to cool a reaction vessel and/or other components ofthe system. Such mechanisms may include, for example, a quenching mode,increased surface area, cooling jacket, venting systems, cold finger,and the like.

In some aspects, the system for making on-site peracid chemistryformulations further comprises an optional controller or softwareplatform. The software platform provides a user or system to select ageneration mode for a desired peracid formulation for on-sitegeneration. As a result, use of the system for onsite peracid chemistrygeneration provides significant user flexibility to generate chemistriesfor particular user-identified purposes. For example, the controller orcontrol software for operation of the system may permit a user or systemto select both the peracid formulation and the desired volume of theformulation for on-site generation. In a further aspect, the controlsoftware may determine the timing, sequencing and/or selection offeeding raw materials (e.g. reagents) into the system, mixing time andtotal reaction time required for production of the user- orsystem-selected peracid formulation.

According to the invention, the controller may further include amechanism for manually starting/stopping any of the same functions,including for example a manual switch panel for the same. In addition tomanual controls, such as a manual switch panel, the controllerpreferably has buttons or other means for selecting particularembodiments according to option displayed by the control softwareplatform. An embodiment of the controller may further include a displayscreen to assist a user in selecting a generation mode for a desiredperacid formulation and any other options for user selection as oneskilled in the art will ascertain based upon the description of theinvention. Concomitant with the control software are user-friendlyinstructions for use displayed on the display screen (or the like).

In an aspect of the invention, the control software utilizes a controlsoftware algorithm to maximize on-site active chemistry yield andprovide safe operating conditions for the reactor vessel(s) of thesystem. The control software permits user-identified chemistryproduction to be run in one or multiple reaction vessels and to properlysequence reactions to obtain active chemistries.

Examples of suitable controllers are disclosed herein, in additionvarious embodiments of those disclosed in U.S. patent application Ser.No. 12/108,202, and U.S. Pat. No. 7,547,421, both entitled Apparatus andMethod for Making Peroxycarboxylic Acid, which are herein incorporatedby reference in their entirety.

In another aspect of the invention, the system may include a data outputmeans for sharing information related to the peroxycarboxylic acidforming compositions and/or peroxycarboxylic acid formulations generatedaccording to the system. For example, an information backbone may beused to both collect and disseminate data from the process of generatingthe peracid formulations including, for example, compositionconsumption, dispensing or usage, and additional formulationproduction-related data. Such data may be generated in real-time and/orprovided in a historical log of operational data detectable or storableby a user or system. In an embodiment of the invention a user or systemis able to monitor usage and performance, including for example,chemistry dispensing, managing chemistry distribution to variouspoint-of-use applications, communication with system operators tocontrol and monitor chemistry dispensing, allocation and/or formulationand the like. According to an additional embodiment of the invention, auser or system is able to control systems, including program systems,remotely.

According to an aspect of the invention, any system operations suitablefor use with the invention may be controlled and/or monitored from aremote location. Remote system operations control and/or monitoring mayfurther include the system updates and/or upgrades. According to anaspect of the invention updates and/or upgrades to system operations maybe downloaded remotely. These and other embodiments of data outputmeans, information sharing, remote system operations and the like, whichmay be adapted for use with the present invention, are furtherdescribed, for example, in U.S. Pat. Nos. 7,292,917, 6,895,307,6,697,706 and 6,377,868 and U.S. Patent Publication Nos. 2005/0102059,2005/0065644, 2004/0088076, 2003/0195657 and 2003/0195656, which arehereby expressly incorporated by reference including, withoutlimitation, the specification, claims, and abstract, as well as anyfigures, tables, or drawings thereof.

In another aspect of the invention, the data output for sharinginformation related to the compositions according to the system maycoordinate multiple systems on at a single site. According to thisembodiment of the invention, information sharing between the multiplesystems may take places place using any communications network capableof coupling one or more systems according to the present invention,including for example, using a server computer and a database.

Illustrated Embodiments

According to an embodiment of the invention, as shown in FIG. 1, a useror process controller input, such as a CIP or tunnel washer processcontroller, selects a peracid formulation desired for on-site generationfor a specific cleaning application. The user or process controllerinput selects both the chemistry formulation and how much is needed(i.e., gallons use solution) and such input information is loaded intothe ABF system. Control software, including a software algorithm, may beused to calculate the timing and sequencing for dosing the raw materialsneeded for the particular peracid chemistry generation. Raw materialsare fed into the reaction vessels of the system under controlled mixtureand reaction times.

As shown in the exemplary and non-limiting FIG. 1, the system may employa variety of measurement devices providing feedback to the system.Measurement devices according to the invention may include devicessuitable to measure one or more reaction kinetics or system operationsfor the generation of peroxycarboxylic acid forming compositions,including for example devices to measure fluorescence, weight, flow,capacitive level, pH, oxidation reduction potential, pressure,temperature and combinations thereof. Such measurement devices maymeasure the system's feed pumps, reaction vessels, reservoir, outlets,etc. Exemplary measurement devices may include the monitoring andreporting of the temperature of the reaction vessels, temperature of theraw materials in the storage drums, etc. Additional measurement devicesmay control: the rate of a mixing component, such as an overhead mixer'sspin rate; the pressure through a regulator (i.e. a regulator affectingthe mixing speed in a reaction vessel); reaction vessel volume; pH ofraw materials and solutions in reaction and/or reservoir storagevessels; timing of the reaction to generate the peroxycarboxylic acidforming compositions; and the like. As one skilled in the art willascertain, such regulators, measurement devices, sensors, etc. are wellknown and are not intended to limit the embodiments of the presentinvention.

In addition, measurement devices may be used to activate alarmsindicating the system and/or methods of generating the ofperoxycarboxylic acid forming compositions are outside of desirableranges; for example, measurement devices may be used to generate out ofproduct alarms (e.g. indicating a raw starting material is ‘low’ or outof product entirely). An exemplary measurement device for such an alarmwould measure the availability of a particular raw material (premix orthe like) from the volume of such raw material in a drum.

Optionally, for generation of a peroxycarboxylic acid formulation (asopposed to the anion peroxycarboxylic acid forming compositions), thestability of the reaction intermediates may be enhanced by adding anacid or aqueous acidic solution. The system provides the user or processcontroller selected peracid formulation for use in a cleaning process,including without limitation, antimicrobial, bleaching, sanitizingand/or antiscaling applications. In addition, various data output andinformation sharing methods may optionally be employed according to themethods and systems of the invention.

Embodiments of the system 20 are further shown in FIGS. 2-5. Theapparatus of the ABF system 20 may comprise one or more reaction vessels22 for the generation of the user or process controller selected peracidformulations. As described according to the invention, the ABF system 20may be configured in single or multiple reaction vessel modes. Notably,a single and/or mixed peracid chemistry can beneficially be producedusing either of the embodiments of the invention—single or multiplereaction vessel systems.

FIG. 2 shows a single reaction vessel embodiment of the invention. Asingle reaction vessel mode is preferred for an individual peracidchemistry. However, single reaction vessel modes may also be used toproduce mixed peracid chemistries. To produce a mixed peracid chemistryin a single reactor model, peracids may be produced through the timedaddition of more than one sugar ester 24 according to the particularhydrolysis reactions to ensure that the reactions are completed at thesame time. According to an embodiment, the raw starting materials 28(optionally including one or more of the sugar esters 24) may becombined in various premixes as opposed to providing each individual rawstarting material 28 from a separate source, as depicted in theexemplary and non-limiting Figures. For clarity the raw startingmaterials 28 depicted in the figures are limited and/or restricted inany fashion to the arrangement and/or particular number of raw startingmaterial 28 vessels (e.g. reagent drum) as shown in the figures. Thenumber of raw starting materials 28 (including the sugar esters 24) usedaccording to the apparatuses and methods of the invention may varyaccording to the various embodiments of the invention disclosed herein.

Sequencing of raw material 28 feeds is critical to producing the correctformulation of peracid-based chemistry. For example, peroxyoctanoic acid(POOA) and peroxyacetic acid (POAA) can be generated through theaddition of the sugar esters 24 sorbitol octanoate and triacetin to areaction vessel 22, respectively, despite the fact the hydrolysisreactions occur at different rates. The POAA reaction takes placequickly (e.g. about 5 minutes) and the POOA reaction takes place at aslower rate (e.g. about 15 minutes). Therefore, timing the addition ofthe sugar ester in excess peroxide at alkaline pH and accurately dosingthe amount of sugar ester can be controlled to generate the desiredperacid chemistry formulation. In particular, the production of themixed peracid system using a single reaction vessel requires theadjustment of the reaction time to produce the POAA concomitantly (or inseries) with the longer reacting POOA.

As a result of the ABF system 20 timing the addition of the sugar esters24 such that the sugar esters 24 are reacted in the same reaction vessel22 for predetermined reaction times and then dispensed from an outlet 36of the reaction vessel 22 or from an outlet 36 of a sump reservoir 34 toa particular cleaning process 38. One skilled in the art shall ascertainbased on the disclosure of the present invention that the generationtime for mixed peracid systems are dependent upon and vary based on theusage rates of the particular raw starting materials, namely the sugaresters.

In addition to the preferred embodiment of using timed addition of rawmaterials for measuring the extent of hydrolysis reactions according tothe invention, alternative embodiments include reactions based uponvolume, weight and/or additional methods to produce a preferredindividual peracid chemistry. The ABF system 20 according to theinvention may use various methods to measure the extent of a reaction,including for example, temperature rise, oxidation reduction potentialand/or pH. The desired peracid systems selected by a user and/or system(including volume of the peracid system) may impact the hydrolysisreactions. However, it is an advantage of the present invention that theABF system accommodates for such variations and changes.

FIG. 3 shows a multiple reaction vessel embodiment of the invention.Multiple reaction vessels 22 may be utilized for on-site generation of amixed peracid system. A second reactor vessel 22 may be run sequentiallyor in parallel. According to the invention, either a user or a controlsoftware initially determines the dosage, mix time and sequencing of rawmaterials 28 (including sugar esters 24) via feed pump 26 into thereaction vessels 22. The proper sequencing and timing ensures that bothperhydrolysis reactions generate reaction intermediates that arecompleted at the same time. Reaction intermediates are then eithercombined in a single reaction vessel 22, pumped to a third or additionalreaction vessel 22 to mix the reaction intermediates, or pumping to areservoir 34 for outlet 36 to a cleaning process 38. Alternatively, thereaction intermediates may be dispensed directly from an outlet 36 ofone or more of the reaction vessels 22.

For any of the exemplary and non-limiting systems depicted in FIGS. 2-5,the apparatus of the ABF system 20 may include a system of feed pumps 26fluidly connecting the sugar esters 24 and other raw starting materials28 to the reaction vessels 22 of the system. The raw starting materials28 may include any raw material source, including for example sugaresters 24, oxidizing agent, alkalinity source, water, catalysts, water,air, etc. According to one embodiment of the invention, the raw startingmaterials 28 are depicted as originating from separate containers orsources. However, as the figures depict non-limiting examples of thesystem, the raw starting materials may be combined, although preferablythe reaction catalyst and precursor sugar ester are provided fromseparate feed pumps 26. According to an embodiment, the raw startingmaterials 28 (optionally including one or more of the sugar esters 24)may be combined in various premixes as opposed to providing eachindividual raw starting material 28 from a separate source, as depictedin the exemplary and non-limiting Figures. Additional description ofsuitable means of supplying the raw starting materials 28 (includingsugar esters 24) are disclosed in further detail in U.S. Pat. No.8,846,107 and U.S. Publication No. 2012/0172441, entitled In SituGeneration of Peroxycarboxylic Acids at Alkaline pH and Methods of UseThereof Feed pumps 26 may feed raw starting materials 28 by varioussuitable mechanisms known to those skilled in the art. According to anembodiment, feed pumps 26 may feed by tick on a flow meter, wherein theflow meter is calibrated in advance. According to an additional aspectof the invention, a positive displacement pump can be used to count pumpstrokes for a diaphragm pump or revolutions for a peristaltic pump.Preferably, feed pumps 26 are calibrated prior to use of the system. Rawmaterials 28 are fed to reaction vessel(s) 22 sequentially or inparallel, as some raw materials 28 maybe fed to the reaction vessel(s)22 at the same time. Raw materials 28 according to the invention includefor example, sugar esters 24, oxidizing agent, alkalinity sources, andwater. The raw materials 28 are mixed in reaction vessel(s) 22 for asufficient period of time for perhydrolysis reaction to take place.

In addition, the ABF system 20 may further comprise an acid or aqueousacidic solution source 18 in fluid communication with the reactionvessels 22, reservoir 34 and/or system outlets 36. According to someaspects of the invention, the system 20 measures the extent of theperhydrolysis reaction to determine when to quench the reaction with theacid or aqueous acidic solution source 18 in order to generate aperoxycarboxylic acid formulation. The addition of the acidulantaccording to the invention increases the solubility of theperoxycarboxylic acid(s). For example, according to the invention, theperoxycarboxylic acid(s) solution may be transported safely without lossof the peracid content. The peroxycarboxylic acid(s) solution mayfurther be diluted to a final use concentration. As one of skill in theart shall ascertain, additional acid may be required for the pH to be inaccordance with the certified levels.

According to the invention, certain measurement devices may be employedto determine the extent of the perhydrolysis reaction for dosing of theacid or aqueous acidic solution source 18. Measurement devices caninclude, for example, time, temperature, oxidation reduction potential,pH, etc. Such devices may measure fluorescence, weight or mass, flow,capacitive level, pH, oxidation reduction potential, pressure,temperature and combinations thereof. Such measurement devices maymeasure the system's feed pumps, reaction vessels, reservoir, outlets,etc., as disclosed herein.

According to the invention, the raw materials 28 are mixed in reactionvessel(s) 22 for a sufficient period of time for perhydrolysis reactionto take place. Various mechanisms for mixing the raw materials may beemployed, including for example, the shape of the reaction vessel (e.g.convex shape at the bottom) designed to assist in mixing its contents,employing mixers (e.g. impellers for circulation within the reactionvessel), circulation pumps, gravity-driven circulation between vessels,and/or combinations. According to a preferred embodiment of theinvention, overhead mixers are preferred for the methods and systems ofthe invention. In particular, overhead mixers are utilized to drive amixing element, such as an impeller mixer, within the reaction vesselaccording to an embodiment of the invention.

Notably, the exemplary ABF system depicted in FIG. 3 showing a multiplereaction vessel embodiment of the invention can further be utilized foron-site generation of a single peracid system. A second reactor vessel22 may be run sequentially or in parallel for generation of a singleperacid system. Such an embodiment is well suited for users wishing toemploy the systems according to the invention and having the option forgenerating both single and mixed peracid systems. For example, a usermay select the generation of a single peracid system (when a multireaction vessel system is employed for on-site generation. According tosuch an embodiment, the same ABF system, as depicted in FIG. 3 may beused for obtaining both single and mixed peracid systems.

FIG. 4 shows a further embodiment of the invention wherein the ABFsystem 20 has multiple reaction vessels 22 to allow the in situacidification to generate a mixed peroxycarboxylic acid formulation. Aseries of feed pumps 26 fluidly connect the source of raw materials 28(including sugar esters 24) to the series of reaction vessels 22 of thesystem 20. The depicted exemplary system of the invention show in FIG. 4reacts a first sugar ester 24 in a first reaction vessel 22 with certainraw materials 28 added sequentially (i.e. an oxidizing agent, and asource of alkalinity). The first reaction vessel can be diluted withwater as a further raw material 28. The reaction temperature can becontrolled using a tank heater 42. For example, according to anembodiment of the invention wherein the perhydrolysis reactions into twosteps (i.e. depicted wherein sugar esters 24 are added to separatereaction vessels 22), the overall temperature of the reaction mixturemay be controlled and is lower. The reaction can be controlled so as tofavor the reaction conditions for formation of each of the percarboxylicacids individually in such an exemplary system. After allowing thereaction mixture to react for a sufficient amount of time in the firstreaction vessel 22, the reaction mixture is transferred to a secondreaction vessel 22 wherein the second sugar ester 24 is added andallowed to react for a sufficient amount of time. Thereafter an acid oraqueous acidic solution source 18 may be added to the second reactionvessel 22.

An exemplary mixed peroxycarboxylic acid system for use of ABF generatorof FIG. 4 is a mixed system of POAA/POOA. According to an embodiment thefirst reaction vessel is used to react esters (e.g. glyceryl octanoate)to produce peroxyoctanoic acid (POOA), using caustic and peroxide.According to an embodiment the caustic and peroxide are blended prior toadding the ester. The reaction vessel is heated slightly above ambientto accelerate production of POOA, preferably between about 32° C. toabout 49° C. (90-100° F.). The second reaction vessel is filled to asub-maximal volume with water prior to adding the POOA from the firstreaction vessel in order to prevent the degradation of theperoxycarboxylic acid and to decrease the temperature of the reactionmixture. The second sugar ester (e.g. triacetin) is introduced into thesecond reaction vessel following the dilution of the POOA reactionmixture solution. The pH remains high (preferably about >12.0) in thesecond reaction vessel and the second ester is reacted to generate POAA.After a sufficient amount of time as passed for the reaction tocomplete, the addition of an acidulant (e.g. acetic acid) lowers the pHto pre-use dilution levels resulting in a solution with increasedstability of the peracids (e.g. up to 5 days), as well as increasedsolubility of the POOA of the mixed peroxycarboxylic acid system.

FIG. 5 shows an expanded view of a controller 50 according to anembodiment of the invention. As depicted, the controller 50 is a part ofthe ABF system 20 for making on-site peracid chemistry formulations asdescribed by various embodiments herein. The controller 50 may also bedescribed as a software platform or as comprising a software platform.As one skilled in the art will ascertain, the ABF system 20 employing acontroller system 50 is not limited to the particular embodimentdepicted in FIG. 5 (i.e. a multiple reaction vessel embodiment of theinvention).

In some aspects the controller 50 may include various components,including for example, a display screen 52 to assist a user in selectingthe various parameters selectable by a user according to the invention.For example, a user views a display screen 52 to view the optionsavailable for a particular generation mode of a desired peracidformulation and any other options for user selection as one skilled inthe art will ascertain based upon the description of the invention.Concomitant with the controller and software 50 are user-friendlyinstructions for use displayed on the display screen 52. In additionalaspects, the controller 50 may further include a means for manuallystarting/stopping any of the same functions, including for example amanual switch panel 56 for the same. In addition to manual controlsdepicted as manual switch panels 56 in FIG. 5, the controller 50preferably also comprises means for selecting 54 options displayed for auser to select on the display screen 52. These and other means for auser to select the various embodiments of the invention are encompassedin the various embodiments of the controller 50.

The controller 50 provides a user or system the flexibility and means toselect a generation mode for a desired peracid formulation for on-sitegeneration according to the invention. The controller providessignificant user flexibility to generate chemistries for particularuser-identified purposes, such as selecting the peracid formulationand/or the desired volume of the formulation for on-site generation. Thesoftware utilized by the controller 50 may further determine the timing,sequencing and/or selection of feeding raw materials 28 (including sugaresters 24) into the system, mixing time and total reaction time requiredfor production of the user- or system-selected peracid formulation.

In some aspects of the invention, reaction intermediates or peracidformulations may be dosed directly from reaction vessel(s) 22 or a sumpreservoir 34 into cleaning process 38 from a system outlet 36.

FIGS. 6A and 6B show diagrams of an embodiment of an adjustable biocideformulator apparatus according to the invention, including descriptionof the dosing of raw starting materials (e.g. reagents) for thegeneration of peracid chemistries according to the invention. Inparticular, FIG. 6A shows a process flow of methods of making theperacid chemistry using the apparatus according to the invention. As setforth, methods of the invention include the steps of peracid generation,a period of reaction holding time followed by evacuation of the line,dilution with water of the concentrated chemistry and optionallyacidification.

FIG. 6B further shows a non-limiting example of a method of peracidchemistry according to FIG. 6A. In the non-limiting example peracidgeneration includes the injection of raw starting materials (e.g.reagents). In particular, the injection of NaOH 12 and water 14 arecombined in injection manifold 21. The injection manifold is not limitedaccording to a particular structure or apparatus. According to apreferred embodiment, the caustic is diluted to a concentration of lessthan or equal to about 20% by weight. The NaOH 12 and water 14 arepreferably homogenized or mixed by passing through a mixer 35.Thereafter, the an ester premix or ester and peroxide 16 are injectedinto another injection manifold 21 of the system. According to thisaspect of the invention the ester premix or ester and peroxide are addedto the dilute NaOH for improved chemistry generation. The ester premixor its individual components 16 are homogenized or mixed 35 with thecaustic stream. Following the mixing, the reagents are held for thereaction to go to completion within a reaction manifold 22. Notably, theholding step can occur directly in a dilution tank 34 or optionally inan intermediate reaction manifold 22. Following the reaction hold timethe reaction manifold 22 is purged with water then air into a dilutionvessel 34 (e.g. line evacuation). Then water 14 is used for the dilutionstep within the dilution tank 34 to dilute the concentrated chemistry.In a further aspect the diluted chemistry can be acidified using an acidor aqueous acid solution 18 within the dilution vessel 34 (or optionallywithin the reaction manifold 22—not depicted in the figure). Uponcompletion of the peracid generation as depicted in FIGS. 6A-B a watersource 14 may be used to flush the system at a high flow rate.

Apparatus Dosing

The apparatus of the ABF system overcomes the raw material feed designchallenge of accurately dosing raw materials. According to theinvention, liquid based raw materials must be dosed into reactionvessel(s) quickly. For example, according to an embodiment of theinvention, the sugar ester is the limiting reaction ingredient andrequires accurate dispensing of the raw material. An example of asuitable sugar ester is sorbital octanoate and/or glyceryl octanoate,which are viscous liquids that are difficult to accurately measure As aresult, pump selection is critical and accommodating pumpcharacteristics with software is a critical embodiment of the ABFsystem.

The dispensing precision required to prepare small batch sizes is morecritical than larger batches, as a result of the dispensing errorbecoming a larger percentage of the dispensed peracid chemistries. As aresult, the apparatus of the ABF system provides feed pumps to reducethe presence of air bubbles in the delivery line altering the amount ofsugar ester chemistry dispensed and reducing the overall yield of thereaction. In addition to providing suitable feed pumps, theconcentration of the sugar ester may be diluted to increase dosingaccuracy. Such methods improve the dosing accuracy and decreasevariations in volumetric flow of reagents according to the invention. Inaddition to the reduction of air bubbles in a delivery line, thedispensing precision according to the invention delivers the reagents ata constant flow rate over long durations of time, thereby reducingand/or eliminating the need for recalibration of the apparatus.

According to an alternative embodiment of the invention, a viscositymodifier may be added to the sugar ester. A viscosity modifier is afurther example of a suitable raw material 28 according to theinvention. Viscosity modifiers according to the invention may be used toadjust the rheology of a reagent in order to reduce the viscosity tomake a raw material more suitable for use in the apparatus and systemaccording to the invention, namely rendering the raw materialsignificantly easier to pump.

An additional embodiment of the invention is to provide the apparatus ofthe ABF system having a vertical alignment of equipment to manage dripsand siphoning. In addition, self checking pumps and foot valves may beused to manage air bubbles. Still further, speed control boards used inware washing applications for rinse aid delivery may be used to slowdown the pumping rate of the reaction limiting sugar esters to improveaccuracy. A skilled artisan will appreciate, based on the disclosure ofthe present invention, additional dosing modifications of the ABF systemencompassed within the scope of the present invention.

Apparatus Rinsing

Rinsing of the ABF system has an impact on yield. According to anembodiment of the invention, adequate rinsing of the reactor vessel(s)and feed pump lines is necessary. According to a preferred embodiment ofthe invention, the control software of the ABF system may be used toestablish a process for system rinsing both reactor vessel(s) and feedpump lines. Remaining water after rinsing or flushing does not have anegative impact on the system. Water remaining in the mixing manifoldimparts a dilution factor for which the dilution factor can beaccommodated in the formulation. However, reaction intermediates must berinsed from the system, as any reacted chemistry not flushed impacts theyield of a subsequent batch. This is a result of residual reactionintermediates in the system imparting unknown actives concentration dueto the instability of the product at high pH over time. In addition,according to an embodiment an air-purge may be further employed afterrinsing of the apparatus according to the invention, which as oneskilled in the art will appreciate effectively removes nearly all liquidcontent from the apparatus after a water rinse.

Preferably, the ABF system, including the reaction vessels, are cleanedbetween batches of peroxycarboxylic acid forming compositions. Accordingto an embodiment of the invention, the system is rinsed (e.g. feed pumplines flushed) with warm/hot water between batches, and/or at regularlyschedules intervals to comply with regulatory requirements (e.g.sanitizing regulations), as one skilled in the art shall ascertain.

Compositions

The embodiments of the invention are suitable for generating theperoxycarboxylic acid chemistries (as well as the anion peroxycarboxylicacid forming compositions) which are disclosed in further detail in therelated U.S. Pat. No. 8,846,107 and U.S. Publication No. 2012/0172441,which are herein incorporated by reference in its entirety. In additionto the chemistries generated, these applications incorporated byreference further disclose the particular raw starting materials (e.g.reagents) suitable for use in the ABF systems according to the inventionto generate the particular chemistries.

In some embodiments, the system according to the present inventionproduces peroxycarboxylic acid forming compositions or peroxycarboxylicacid compositions for use in a variety of cleaning applications. Thecompositions have enhanced stability. According to an embodiment of theinvention, the peroxycarboxylic acid forming compositions are stable forup to 24 hours providing suitable stability for on-site generation andusage for a variety of cleaning applications. According to a furtherembodiment, the peroxycarboxylic acid compositions are stable for up toat about 7 to 10 days.

In some aspects, the present disclosure relates to peroxycarboxylic acidforming compositions. That is, the compositions are capable ofgenerating peroxycarboxylic acids in situ, in a non-equilibriumreaction. Surprisingly, it has been found that the optimum pH for thegeneration of peroxycarboxylic acid compositions is greater than about12, or pH greater than about 13. It has also been found that mixedperoxycarboxylic acid compositions, viz. compositions that form two ormore peroxycarboxylic acids, can be generated in situ in accordance withthe methods disclosed herein. Peroxycarboxylic (or percarboxylic) acidsgenerally have the formula R(CO₃H)n, where, for example, R is an alkyl,aryl alkyl, cycloalkyl, aromatic, or heterocyclic group, and n is one,two, or three, and named by prefixing the parent acid with peroxy. The Rgroup can be saturated or unsaturated as well as substituted orunsubstituted.

In an embodiment of the invention the peroxycarboxylic acid formingcompositions comprise individual reagents combined according to theinvention. These reagents are described herein individually along andinclude at least one ester of a polyhydric alcohol and a C1 to C18carboxylic acid, an oxidizing agent, a source of alkalinity, solvents,and other functional groups. An acidulant is also described herein as areagent to be added to the compositions after the formation of thepercarboxylic acid(s). Alternatively, as described herein, there may bebenefits to providing the reagents in various premix formulations todecrease the number of reagents and/or increase the simplicity of theinvention. Each of these embodiments are described in further detailherein.

Esters

In some aspects, the compositions include an ester of a polyhydricalcohol and a C1 to C18 carboxylic acid. According to an embodiment, thepolyhydric alcohol may also include a sugar alcohol. The compositionscan also include more than one or a mixture of esters of a polyhydricalcohol and a C1 to C18 carboxylic acid. For example, in someembodiments, the compositions include two, three or four esters. Whenmore than one ester is present, the esters can be different. Forexample, in some embodiments, the compositions can include a first esterof a polyhydric alcohol and a C1 to C4 carboxylic acid, and a secondester of a polyhydric alcohol and a C5 to C11 carboxylic acid. Forfurther example, in some embodiments, the compositions can include afirst ester of a polyhydric alcohol and a C1 to C18 carboxylic acid in amono, di or tri-formation, and a second ester of a polyhydric alcoholand a C1 to C18 carboxylic acid in a mono, di or tri-formation. Oneskilled in the art will appreciate the various combinations of estersthat can be used for the compositions according to the invention.

An example of a suitable ester for use according to the invention isglycerol octanoate. Glycerol octanoate has multiple ester components andothers, including glycerol monooctanoate, glycerol dioctanoate, glyceroltrioctanoate and others (glycerin, fatty acid, water). An estimatedcomponent percentage of each is approximated at about 39.6% glycerolmonooctanoate, 24.5% glycerol dioctanoate, 1.42% glycerol trioctanoateand 34.5% of the others (glycerin, fatty acid, water).

The use of various forms of an ester (e.g. mono, di and/ortri-formations) to comprise a mixture of esters will impact the peracidyield of a particular composition according to the invention. Forexample, the various forms of the ester will have different kinetics ingenerating the peracids according to the methods of the invention. Forexample, in one aspect, a monooctanoate glycerol ester is faster ingenerating peracid than the di- or trioctanoate glycerol esters. Inaddition, the selection of the various forms of an ester will be furtherimpacted by the water solubility of the compositions and whether anyadditional ingredients are combined to affect solubility (e.g. solvents)that would favor the use of less soluble ester forms (e.g.tri-formations). Accordingly, one skilled in the art of reactionkinetics will ascertain the benefits of using various combinations ormixtures of esters according to the compositions and methods of theinvention.

The esters for use in the present invention include esters of polyhydricalcohols with carboxylic acid based leaving groups. A variety ofcarboxylic acids can be included. Carboxylic acids generally have theformula R(COOH)n, where, for example, R is an alkyl, aryl alkyl,cycloalkyl, aromatic, or heterocyclic group, and n is one, two, orthree. In some embodiments, the carboxylic acid leaving group is a C₅ toC₁₁ carboxylic acid. In some embodiments, the carboxylic acid leavinggroup is a C₁ to C₄ carboxylic acid. In other embodiments, thecompositions include two esters of polyhydric alcohols, each esterhaving a different carboxylic acid leaving group. For example, thecompositions can include a polyhydric alcohol ester with a C1 to C4carboxylic acid leaving group, and also include a polyhydric alcoholester with a C5 to C11 carboxylic acid leaving group.

Examples of suitable carboxylic acids include, but are not limited to,formic, acetic, propionic, butanoic, pentanoic, hexanoic, heptanoic,octanoic, nonanoic, decanoic, undecanoic, dodecanoic, as well as theirbranched isomers, lactic, maleic, ascorbic, citric, hydroxyacetic,neopentanoic, neoheptanoic, neodecanoic, oxalic, malonic, succinic,glutaric, adipic, pimelic subric acid, and mixtures thereof.

Without wishing to be bound by any particular theory, it is thought thatthe esters included in the compositions undergo a perhydrolysisreaction, thereby forming the peroxycarboxylic composition. An exemplaryperhydrolysis reaction in accordance with the present disclosure isillustrated below:

As can be seen from this illustration, it is thought the oxidizingagent, H₂O₂, perhydrolyzes the ester bond, thereby forming thepercarboxylic acid corresponding to the cleaved carboxylic acid group.In contrast to an acid catalyzed equilibrium reaction, the reaction isstoichiometric, i.e. no excess amounts of the reactants are required forthe reaction. The kinetics of the reaction are pH dependent, and thereaction can reach the maximum yield in the order of minutes. Esterssuitable for use include, but are not limited to, monooctanoicglyceride, dioctanoic glyceride, trioctaonoic glyceride, polyglyceroloctanoate, sorbitan monooctanoate, sorbitan dioctanoate, sorbitantrioctanoate, laurate sucroside and mixtures and derivatives thereof.

The compositions include the esters in an amount sufficient to generatethe desired amount of percarboxylic acid. In some embodiments, thecompositions include about 0.01 wt-% to about 95 wt-% of the ester,about 0.1 wt-% to about 50 wt-% of the ester, or about 1 wt-% to about10 wt-% of the ester. In some embodiments, more than one ester ispresent in the compositions. Each ester can be present in thecompositions at the above stated weight percents.

Unlike conventional acid catalyzed equilibrium peroxycarboxylic acidforming compositions, the compositions of the present invention can beformed using a non-equilibrium perhydrolysis reaction. Thus, an excessamount of the starting reagents is not needed. Accordingly, afterformation of the peroxycarboxylic acid, the compositions contain lesscarboxylic acid and more peroxycarboxylic acid than an equivalentequilibrium reaction. In some embodiments, the compositions containabout 1 part percarboxylic acid for every about 1 part carboxylic acidafter perhydrolysis, or about 6 part percarboxylic acid for every about1 part carboxylic acid after perhydrolysis. In some embodiments, thecompositions are free of or substantially free of carboxylic acids afterthe perhydrolysis reaction.

Alkalinity Source

The compositions also include a source of alkalinity. The source ofalkalinity can include, but is not limited to, an alkaline metalhydroxide, an alkaline earth metal hydroxide, an alkali metal silicate,an alkali metal carbonate, borates and mixtures thereof. Suitablealkaline metal hydroxides include, but are not limited to, sodiumhydroxide, potassium hydroxide and mixtures thereof. Suitable alkalineearth metal hydroxides include, but are not limited to, magnesiumhydroxide, calcium hydroxide and mixtures and derivatives thereof.Suitable alkali metal silicates include but are not limited to, sodiumsilicate and derivatives thereof. In other embodiments, an alkali metalcarbonate can be used as a source of alkalinity. For example, in someembodiments, sodium carbonate, sodium bicarbonate or mixtures andderivatives thereof can be used.

The source of alkalinity can be present in the compositions in an amountsufficient to provide the desired pH. In some embodiments, thecompositions have a pH greater than about 12, greater than about 12.5,or greater than about 13. In some embodiments, the alkaline source ispresent in the composition from about 0.001 wt-% to about 50 wt-%, fromabout 1 wt-% to about 30 wt-%, or about 10 wt-% to about 25 wt-%. Insome embodiments, the alkaline source is present at from about 25 wt-%to about 50 wt-% of the composition. It is to be understood that allranges and values between these ranges and values are encompassed by thepresent disclosure.

Oxidizing Agent

The compositions also include an oxidizing agent. The oxidizing agentmay include a peroxide source. Oxidizing agents suitable for use withthe compositions include the following types of compounds or sources ofthese compounds, or alkali metal salts including these types ofcompounds, or forming an adduct therewith: hydrogen peroxide,urea-hydrogen peroxide complexes or hydrogen peroxide donors of: group 1(IA) oxidizing agents, for example lithium peroxide, sodium peroxide;group 2 (IIA) oxidizing agents, for example magnesium peroxide, calciumperoxide, strontium peroxide, barium peroxide; group 12 (IIB) oxidizingagents, for example zinc peroxide; group 13 (IIIA) oxidizing agents, forexample boron compounds, such as perborates, for example sodiumperborate hexahydrate of the formula Na₂[B₂(O₂)₂(OH)₄].6H₂O (also calledsodium perborate tetrahydrate); sodium peroxyborate tetrahydrate of theformula Na₂B₂(O₂)₂[(OH)₄].4H₂O (also called sodium perboratetrihydrate); sodium peroxyborate of the formula Na₂[B₂(O₂)₂(OH)₄] (alsocalled sodium perborate monohydrate); group 14 (IVA) oxidizing agents,for example persilicates and peroxycarbonates, which are also calledpercarbonates, such as persilicates or peroxycarbonates of alkalimetals; group 15 (VA) oxidizing agents, for example peroxynitrous acidand its salts; peroxyphosphoric acids and their salts, for example,perphosphates; group 16 (VIA) oxidizing agents, for exampleperoxysulfuric acids and their salts, such as peroxymonosulfuric andperoxydisulfuric acids, and their salts, such as persulfates, forexample, sodium persulfate; and group VIIa oxidizing agents such assodium periodate, potassium perchlorate. Other active inorganic oxygencompounds can include transition metal peroxides; and other suchperoxygen compounds, and mixtures thereof.

In some embodiments, the compositions of the present invention employone or more of the inorganic oxidizing agents listed above. Suitableinorganic oxidizing agents include ozone, hydrogen peroxide, hydrogenperoxide adduct, group IIIA oxidizing agent, or hydrogen peroxide donorsof group VIA oxidizing agent, group VA oxidizing agent, group VIIAoxidizing agent, or mixtures thereof. Suitable examples of suchinorganic oxidizing agents include percarbonate, perborate, persulfate,perphosphate, persilicate, or mixtures thereof.

In some embodiments, the oxidizing agent includes hydrogen peroxide, ora source or donor of hydrogen peroxide. In other embodiments, theoxidizing agent includes a peroxide source selected from a percarbonate,a perborate urea hydrogen peroxide, PVP-peroxides and mixtures thereof.

The compositions may contain an effective amount of an oxidizing agent.In some embodiments, the compositions include about 0.001 wt-% to about60 wt-% of the oxidizing agent, or about 1 wt-% to about 25 wt-% of theoxidizing agent. In some embodiments, the compositions include about 30wt-% to about 50 wt-% of the oxidizing agent. It is to be understoodthat all ranges and values between these ranges and values areencompassed by the present invention.

Solvent

In some embodiments, the compositions of the invention further include asolvent. In some embodiments, the solvent is water. The water may beprovided by the use of aqueous reagents, viz. oxidizing agent,alkalinity source. In other embodiments, an additional amount of wateris added to the compositions. The compositions may be free of orsubstantially free of any added water. A non-aqueous solvent may also beused in the compositions. For example, in some embodiments, an alcoholis included as a solvent in the compositions.

The compositions may include an effective amount of solvent. In someembodiments, the compositions may include about 10 wt-% to about 99 wt-%of a solvent, or about 20 wt % to about 80 wt-% of a solvent. In otherembodiments, the compositions may include more than about 30 wt-%, morethan about 50 wt-%, more than about 60 wt-% or more than 70% of asolvent. It is to be understood that all values and ranges between thesevalues and ranges are encompassed by the present invention.

Eliminated Functional Ingredients

Unlike conventional equilibrium based peroxycarboxylic acidcompositions, the compositions disclosed herein are formed from anon-equilibrium reaction. Further, the composition disclosed herein canbe used immediately after generation. Thus, many of the additionalingredients required in equilibrium based compositions do not need to beincluded in the present compositions. In some embodiments stabilizingagents are preferred for certain compositions according to the inventionand provide benefits. However, beneficially, the use of non-equilibriumchemistry according to the present invention optionally provides thatthe compositions can be free of, or substantially free of a stabilizingagent.

Stabilizing agents are commonly added to equilibrium peroxycarboxylicacid compositions to stabilize the peracid and hydrogen peroxide andprevent the decomposition of these constituents within the compositions.Various embodiments of the invention do not require the use of at leastone or more of such stabilizing agents. Examples of stabilizing agentsmay include for example, surfactants, couplers, hydrotropes, acidcatalysts and the like that are conventionally used in equilibriumperacid compositions to stabilize and improve shelf life of thecomposition.

Further examples of stabilizing agents include, for example, chelatingagents or sequestrants. Such sequestrants include, but are not limitedto, organic chelating compounds that sequester metal ions in solution,particularly transition metal ions. Such sequestrants include organicamino- or hydroxy-polyphosphonic acid complexing agents (either in acidor soluble salt forms), carboxylic acids (e.g., polymericpolycarboxylate), hydroxycarboxylic acids, aminocarboxylic acids, orheterocyclic carboxylic acids, e.g., pyridine-2,6-dicarboxylic acid(dipicolinic acid). Dipicolinic acid, 1-hydroxyethylidene-1,1-diphosphonic acid (CH3C(PO3H2)2OH) (HEDP) are furtherexample of stabilizing agents.

Additional examples of stabilizing agents commonly used in equilibriumchemistry to stabilize the peracid and hydrogen peroxide and/or preventthe premature oxidation of the composition include phosphonic acid orphosphonate salt. Phosphonic acids and phosphonate salts include HEDP;ethylenediamine tetrakis methylenephosphonic acid (EDTMP);diethylenetriamine pentakis methylenephosphonic acid (DTPMP);cyclohexane-1,2-tetramethylene phosphonic acid; amino[tri(methylenephosphonic acid)]; (ethylene diamine[tetra methylene-phosphonic acid)];2-phosphene butane-1,2,4-tricarboxylic acid; or salts thereof, such asthe alkali metal salts, ammonium salts, or alkyloyl amine salts, such asmono, di, or tetra-ethanolamine salts; picolinic, dipicolinic acid ormixtures thereof. In some embodiments, organic phosphonates, e.g., HEDPare well known as used stabilizing agents.

Exemplary commercially available food additive chelating agents includephosphonates sold under the trade name DEQUEST® including, for example,1-hydroxyethylidene-1,1-diphosphonic acid, available from MonsantoIndustrial Chemicals Co., St. Louis, Mo., as DEQUEST® 2010;amino(tri(methylenephosphonic acid)), (N[CH₂PO₃H₂]₃), available fromMonsanto as DEQUEST® 2000; ethylenediamine[tetra(methylenephosphonicacid)] available from Monsanto as DEQUEST® 2041; and2-phosphonobutane-1,2,4-tricarboxylic acid available from Mobay ChemicalCorporation, Inorganic Chemicals Division, Pittsburgh, Pa., as BayhibitAM. Further exemplary sequestrant can be or include aminocarboxylic acidtype sequestrant. Suitable aminocarboxylic acid type sequestrantsinclude the acids or alkali metal salts thereof, e.g., amino acetatesand salts thereof. Suitable aminocarboxylates includeN-hydroxyethylaminodiacetic acid; hydroxyethylenediaminetetraaceticacid, nitrilotriacetic acid (NTA); ethylenediaminetetraacetic acid(EDTA); N-hydroxyethylethylenediaminetriacetic acid (HEDTA);diethylenetriaminepentaacetic acid (DTPA); and alanine-N,N-diaceticacid; and the like; and mixtures thereof. Still further sequestrantsinclude polycarboxylates, including, for example, polyacrylic acid,maleic/olefin copolymer, acrylic/maleic copolymer, polymethacrylic acid,acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide,hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamidecopolymers, hydrolyzed polyacrylonitrile, hydrolyzedpolymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrilecopolymers, polymaleic acid, polyfumaric acid, copolymers of acrylic anditaconic acid, phosphino polycarboxylate, acid or salt forms thereof,mixtures thereof, and the like.

Further, unlike conventional equilibrium based peroxycarboxylic acidcompositions, the present compositions can also be free of, orsubstantially free of surfactants. This is especially advantageous forcompositions incorporating C5 to C18 peroxycarboxylic acids. That is,under perhydrolysis conditions, the C5-C18 peroxycarboxylic acid anionsgenerated are water soluble. If the anions (e.g. peroxycarboxylicacid-forming compositions) are acidified for end use applications, theconcentrations of peroxycarboxylic acids are below the water solubilitylimit of the peroxycarboxylic acids. Thus, couplers are not needed tocouple the peroxycarboxylic acids in solution.

Additional Functional Ingredients

The compositions may also include additional functional ingredients.Additional functional ingredients suitable for use in the presentcompositions include, but are not limited to, acidulants, hydrotropes,dispersants, antimicrobial agents, optical tracers, solidificationagent, aesthetic enhancing agent (i.e., colorant (e.g., pigment),odorant, or perfume), among any number of constituents which can beadded to the composition. For example, suitable functional ingredientsfor various embodiments of the invention are hydrotropes, which may bedesired for producing clear compositions or dispersants which are moreefficient in producing homogeneous dispersions. Such adjuvants can bepreformulated with the present compositions or added to the compositionsafter formation, but prior to use. The compositions can also contain anynumber of other constituents as necessitated by the application, whichare known and which can facilitate the activity of the presentcompositions.

Acidulant

In an embodiment, the present compositions can include an acidulant. Theacidulant can be added to the compositions after the formation of thepercarboxylic acid. That is, an acidulant can be added to theperoxycarboxylic acid concentrate to form an acidified use solution. Theacidulant can be effective to form a use composition with pH of about 1or less. The acidulant can be effective to form a use composition withpH of about 8, about 8 or less, about 7, about 7 or less, about 6, about6 or less, about 5, about 5 or less, or the like. In some embodiments,the acidulant is present at an amount effective to form a use solutionwith a pH of about 6 to about 8, about 1 to about 8, or about 1 to about5. In a further embodiment, the acidulant may be added to a semi-dilutedreaction solution to produce meta-stable peracid composition.

Any suitable acid can be included in the compositions as an acidulant.In an embodiment the acidulant is an acid or an aqueous acidic solution.In an embodiment, the acidulant includes an inorganic acid. In someembodiments, the acidulant is a strong mineral acid. Suitable inorganicacids include, but are not limited to, sulfuric acid, sodium bisulfate,phosphoric acid, nitric acid, hydrochloric acid. In some embodiments,the acidulant includes an organic acid. Suitable organic acids include,but are not limited to, methane sulfonic acid, ethane sulfonic acid,propane sulfonic acid, butane sulfonic acid, xylene sulfonic acid,cumene sulfonic acid, benzene sulfonic acid, formic acid, acetic acid,mono, di, or tri-halocarboyxlic acids, picolinic acid, dipicolinic acid,and mixtures thereof. In some embodiments, the compositions of thepresent invention are free or substantially free of a phosphorous basedacid.

In an embodiment, the acidulant includes a carboxylic acid with pK_(a)less than 5. Suitable carboxylic acids with pK_(a) less than 5 includeacetic acid, hydroxyacetic acid, hydroxypropionic acid, otherhydroxycarboxylic acids, mixtures thereof, or the like. Such anacidulant is present at a concentration where it does not act as asolubilizer. In some embodiments, the compositions are free of, orsubstantially free of a carboxylic acid.

In certain embodiments, the present composition includes about 0.001 toabout 50 wt-% acidulant, about 0.001 to about 30 wt-% acidulant, about 1to about 50 wt-% acidulant, about 1 to about 30 wt-% acidulant, about 2to about 40 wt-% acidulant, about 2 to about 10 wt-% acidulant, about 3to about 40 wt-% acidulant, about 5 to about 40 wt-% acidulant, about 5to about 25 wt-% acidulant, about 10 to about 40 wt-% acidulant, about10 to about 30 wt-% acidulant, about 15 to about 35 wt-% acidulant,about 15 to about 30 wt-% acidulant, or about 40 to about 60 wt-%acidulant. The composition can include any of these ranges or amountsnot modified by about.

Premix Formulations

In an embodiment, the reagents described herein (e.g. at least one esterof a polyhydric alcohol and a carboxylic acid, source of alkalinity,oxidizing agent) may be combined into various premix formulations toreduce the number of raw starting materials required for the methods andcompositions and further simplify the methods of the invention.According to such an embodiment the providing of premix formulationsensures consistent and stable delivery of reagents.

Premix formulations suitable for use according to the invention maycomprise, consist of and/or consist essentially of at least one ester,an oxidizing agent and mixtures thereof. Premix formulations suitablefor use according to the invention may comprise, consist of and/orconsist essentially of at least one ester, an oxidizing agent, a solventand mixtures thereof. Premix formulations suitable for use according tothe invention may also comprise, consist of and/or consist essentiallyof at least one ester, an oxidizing agent, water, solvents, dispersingagents, and mixtures thereof.

As one skilled in the art will ascertain the use of premixes employsadditional function ingredients for purpose of stabilizing the premixconcentrate for use in the compositions and methods according to theinvention. For example, hydrotropes, dispersing agents and/or othersolvents may be desirable for maintaining the solubility and stabilityof a particular concentrated premix. The use of any couplers ordispersing agent (such as a surfactant) within a premix formulation isdistinct from the use of surfactants in the conventional generation andstorage of peracid chemistries, wherein couplers are critical toestablishing and maintaining a stable, clear solution of the generatedperacid chemistry.

According to the invention, the use of dispersing agents alone within aconcentrated premix formulation does not stabilize the premixcomposition. Rather the dispersing agents are provided in an amountsuitable for providing meta-stable peracid compositions generated fromthe premix after acidification, before further dilution for application.The most efficient dispersing agents were found to be anionicsurfactants, and this type of surfactant is known to have high foamingprofile. For applications which involves mechanical actions (e.g. CIPsanitizing), the high foam property of the composition is undesirable.Thus, in addition to economic reason, it is preferred to use a minimumamount of the dispersing agent to achieve a meta-stable peracidcomposition to meet the application of use requirements.

According to an embodiment of the invention less than about 10 ppm,preferably less than about 9 ppm, less than about 8 ppm, less than about7 ppm, less than about 6 ppm, less than about 5 ppm, less than about 4ppm, less than about 3 ppm, less than about 2 ppm, or less than about 1ppm of a dispersing agent is included in the generated peracid chemistryas a result of the use of a surfactant dispersing agent in aconcentrated premix formulation according to the invention. This isdistinct from the level of surfactants in use solutions of a traditionalperacid chemistry, where the amounts of surfactants are normally inexcess of about 50 ppm, in excess of about 60 ppm, in excess of about 70ppm, in excess of about 80 ppm, in excess of about 90 ppm, or in excessof about 100 ppm.

According to a further embodiment of the invention less than about 2%dispersing agent is present in the premix composition, wherein at leastabout 5%, about 6%, about 7%, about 8% or about 9% are required toprovide the stable, clear solution of a generated peracid chemistry whenacidified. This is distinct from the generated peracid chemistryaccording to the invention wherein a meta stable chemistry is generated.Although not wishing to be limited to a particular theory of mechanismof action of the invention, the generated meta-stable composition is amilky colored composition having stability for at least a few hours.

According to an embodiment of the invention, the use of a solvent (e.g.ethanol) is an efficient way to make a stable premix composition.Solvents suitable for the concentrated premix formulations according tothe invention include, for example, organic solvents such as alcohol,ether or ketone. Preferably, the solvent is a water soluble alcohol,such as ethanol, methanol, propanol, isopropanol and/or butanol. As oneskilled in the art will ascertain the various isomers of the solvents,including alcohols, are further included within the scope of thesolvents suitable for use with the concentrated premix formulations ofthe invention.

Beneficially, the use of concentrated premix formulation still does notrequire the use of any chelators and/or stabilizers. As a result,regardless of whether individual reagents or concentrated premixformulations are utilized according to the invention, both the reagentsand the peracid compositions generated according to the inventionprovide sustainable chemistries as a result of the elimination of theuse of various stabilizers and/or additional amounts of chemistryrequired to drive the formation of traditional peracid chemistry. As aresult of reduced input of reagents for the compositions according tothe invention (e.g. resulting from the use of a non-equilibriumreaction) there is a significantly reduced waste stream (e.g. anyreagents and/or percentage of composition not impacting themicro-efficacy of the compositions). Instead the present inventionprovides increased amounts of post-reaction products (e.g. peracids)with decreased amounts of unreacted reagents.

In an aspect of the invention, a premix formulation may deliver theester of a polyhydric alcohol and a carboxylic acid and the oxidizingagent. In one aspect a premix formulation includes an ester of apolyhydric alcohol and a carboxylic acid, an oxidizing agent and adispersing agent. In another aspect a premix formulation includes anester of a polyhydric alcohol and a carboxylic acid, an oxidizing agent,a dispersing agent and water.

Suitable dispersing agents for use according to the concentrated premixformulations of the invention include polymers, surface active agents orany compounds which will help to achieve a meta-stable solution afterthe ester perhydrolysis through the interaction with the peroxy fattyacids generated through perhydrolysis. These may include, for example,sulfonated oleic acids (SOA), 1-octanesulfonic acid (NAS), sodium laurylsulfonates (SLS) and the like. In another aspect a premix formulationincludes an ester of a polyhydric alcohol and a carboxylic acid, anoxidizing agent and a solvent. Ethanol and methanol are examples ofsuitable solvents for use in stabilizing the concentrated premixformulation according to the invention. The use of the solvent incertain embodiments obviates the use of a dispersing agent for premixstability. However, in alternative embodiments a premix formulation mayinclude an ester of a polyhydric alcohol and a carboxylic acid, anoxidizing agent, a dispersing agent and a solvent. Without wishing to belimited to a particular theory or mechanism of action of the invention,the combined use of a dispersing agent and a solvent within aconcentrated premix formulation reduces the overall need for asurfactant dispersing agent in the premix composition.

In still another aspect a concentrated premix formulation includes anoxidizing agent and a dispersing agent.

In certain embodiments, the concentrated premix composition includesabout 0.001 to about 90 wt-% ester of the polyhydric alcohol and acarboxylic acid, about 0.1 to about 90 wt-% ester, about 1 to about 75wt-% ester, about 10 to about 75 wt-% ester, about 25 to about 75 wt-%ester, about 30 to about 70 wt-% ester, or about 30 to about 65 wt-%ester.

In certain embodiments, the concentrated premix composition furtherincludes about 0.001 to about 99 wt-% oxidizing agent, about 0.1 toabout 95 wt-% oxidizing agent, about 1 to about 90 wt-% oxidizing agent,about 2.5 to about 60 wt-% oxidizing agent, about 5 to about 50 wt-%oxidizing agent, or about 10 to about 40 wt-% oxidizing agent.

In certain embodiments, the concentrated premix composition furtherincludes about 0.001 to about 50 wt-% dispersing agent, about 0.1 toabout 40 wt-% dispersing agent, about 1 to about 30 wt-% dispersingagent, about 5 to about 30 wt-% dispersing agent, about 5 to about 20wt-% dispersing agent, or about 5 to about 15 wt-% dispersing agent. Theamount of dispersing agent is selected to ensure that only enoughdispersing agent to obtain a meta-stable solution after perhydrolysisand acidification. Beneficially according to the invention, the premixformulations do not contain sufficient dispersing agent to obtain a onephase premix solution.

In certain embodiments, the concentrated premix composition furtherincludes about 0.001 to about 80 wt-% solvent, about 0.1 to about 40wt-% solvent, about 1 to about 30 wt-% solvent, about 5 to about 30 wt-%solvent, about 5 to about 20 wt-% solvent, or about 5 to about 15 wt-%solvent. 3 The level of solvent is selected to ensure the sufficientamount to solubilize the ester(s) of polyhydric alcohol in theconcentrated premix formulation. As one skilled in the art willascertain the amount of solvent required for such solubilization willvary depending upon the type and level of ester(s) in the premixcomposition.

In certain embodiments, the concentrated premix composition furtherincludes about 0.001 to about 90 wt-% water, about 0.1 to about 80 wt-%water, about 1 to about 75 wt-% water, about 5 to about 60 wt-% water,about 10 to about 50 wt-% water, or about 20 to about 40 wt-% water. Thepremix compositions can include any of these ranges or amounts,including those not modified by about.

The pH of the concentrated premix formulation according to the inventionis preferably between 2 and about 10, preferably between about 3 andabout 9, and more preferably between about 5 and about 7. Thereafter thepH of the premix formulation is combined with an a source of alkalinityto increase the pH to a pH greater than about 12, greater than about12.5, or greater than about 13 according to the invention.

Methods of Making Peracid Compositions

In some aspects, the present disclosure provides methods for on-sitegeneration of the peroxycarboxylic acid forming compositions andperoxycarboxylic acid disclosed herein. According to an embodiment ofthe invention, the methods of on-site generation are particularlysuitable for batch preparation (i.e. batch mode) of peroxycarboxylicacid forming compositions and peroxycarboxylic acids. Batch preparationsare most desirable for on-site production having intermittent needs forthe peroxycarboxylic acid forming compositions and peroxycarboxylicacids. However, as one skilled in the art will ascertain, the methods ofon-site generation may be modified to provide continuous production ofthe peroxycarboxylic acid forming compositions and peroxycarboxylicacids.

The method includes combining at least one ester of a polyhydric alcoholand a C1 to C18 carboxylic acid, a source of alkalinity and an oxidizingagent in a reaction vessel. The method may include inputting a user- orsystem-controlled peroxycarboxylic acid forming composition orperoxycarboxylic acid formulation that is desired for a particular use.The user- or system-controlled input may be put into a control softwarefor an adjustable biocide formulator or generator system, wherein saidinput formulation selects an individual or mixed peroxycarboxylic acidforming composition or peroxycarboxylic acid and the correspondingvolume or mass of the chemistry for onsite generation.

In some embodiments a user controls the input for the on-site chemistrygeneration. In further embodiments, a system-controlled input mayinclude, for example, a CIP process, bottle washer, aseptic filler,vegetable wash or rinse sink, 3^(rd) sink sanitizing sink, textilebleaching process and combinations thereof.

In some embodiments, the user- or system-input selects either a singleor multiple reaction vessel mode for the peroxycarboxylic acid and/ormixed peroxycarboxylic acid or peroxycarboxylic acid forming compositiongeneration. As a result of the reaction vessel mode selected by theinput, the addition of the reaction reagents, including at least theesters, source of alkalinity and oxidizing agent, may be added inparallel or sequentially. The reagents can be combined in any suitablemanner according to the invention and mixed for an amount of timeeffective to form the desired percarboxylic acid forming composition orpercarboxylic acid concentration.

According to the invention, reagents may be added substantiallysimultaneously to a single reaction vessel, and mixed for an amount oftime effective to form the desired concentration. Alternatively,reagents may be added sequentially to a single reaction vessel orseparate reaction vessels. Still further, reagents may be combined fromseparate reaction vessels into an additional reaction vessel or areservoir (e.g. dilution tank).

In some embodiments, the pH of the reaction mixture is greater thanabout 12. In other embodiments, the reaction mixture is greater thanabout 12.5, or greater than about 13.

According to an embodiment of the invention, the reagents are mixed inone or more reaction vessels for a period of time sufficient for theperhydrolysis reaction to occur. In some embodiments, the reagents aremixed for about 5 to about 30 minutes. In other embodiments, thereagents are mixed for about 10, about 15, about 20, or about 25minutes. The mixing may take place using a variety of mixing mechanisms,including for example, an impeller or a mechanical blade mixer, such asa mixer having a variable speed control motor to achieve homogeneousblending of reagents.

In additional preferred embodiments the mix order of reagents arecontrolled to produce a consistent output of peracid chemistry withoutany fouling (e.g. precipitation) of the reagents. In one aspect of theinvention, the source of alkalinity (e.g. sodium hydroxide or causticsoda) is combined with water (e.g. diluted) prior to the addition of theester source. As disclosed herein the ester source can further beprovided in an ester premix (e.g. ester/peroxide premix).

The concentration of reagents, in addition to mixing order, can furtherbe used to control the production of the percarboxylic acid composition.In a preferred embodiment, the concentration of the source of alkalinityis diluted to produce a consistent output of chemistry without anyfouling (e.g. precipitation) of the reagents. In one aspect theconcentrated alkaline solution (e.g. NaOH) is diluted with a watersource before the ester component is combined with the reagents.Although not intending to be limited according to any theory of theinvention and/or mechanism of action, the invention demonstratessuperior chemistry generation when a system delivers a source ofalkalinity (e.g. NaOH solution) that is no more than about 50%,preferably no more than about 40% on an actives basis before combiningwith the ester reagent to initiate the peracid production reaction.

According to preferred methods of making the peracid chemistry, anex-situ ABF generator system using a injection manifold to combine analkaline source, an ester precursor, a peroxygen source and optionallywater for production of a peroxy acid is used. Preferably the alkalinesource is caustic soda, wherein the caustic stream feeding the manifoldis diluted. In an aspect the caustic can be diluted within the manifoldto the target concentration of less than about 50%, preferably less thanabout 40% by weight. In an additional embodiment, the ester is added tothe system downstream (e.g. after the addition of the diluted NaOHsolution).

In an embodiment, the extent of the ester perhydrolysis reaction ismeasured using one or more measurement devices. Suitable measurementdevices measures one or more reaction kinetics or system operations,including for example fluorescence, weight, flow, capacitive level, pH,oxidation reduction potential, pressure, temperature and combinationsthereof, as disclosed herein. According to an embodiment, themeasurement devices may be used to determine the need and/or timing toadd an acid or aqueous acidic solution to dilute the peroxycarboxylicacid forming composition to form the peroxycarboxylic acid composition.In some embodiments the addition of an acid or aqueous acidic solutiondecreases the pH of the reaction mixture from greater than about 12 to aneutralized pH of about 1.0 to about 8.0.

In an embodiment of the invention, the peroxycarboxylic acid formingcomposition is dispensed for use in a cleaning process. According to anembodiment, the peroxycarboxylic acid forming composition may begenerated in batches approximately at least about every 15 minutes,preferably about every 10 minutes, and more preferably about every 5minutes. An acid or aqueous acidic solution may be added to theperoxycarboxylic acid forming composition outside of the systemaccording to the invention.

Preferably, the ABF system, including the reaction vessels, are cleanedbetween batches of peroxycarboxylic acid forming compositions. Rinsingof the ABF system is expected to have an impact on yield of theperoxycarboxylic acid forming compositions. According to an embodimentof the invention, the system is rinsed (e.g. feed pump lines flushed)with warm/hot water between batches, and/or at regularly schedulesintervals to comply with regulatory requirements (e.g. sanitizingregulations), as one skilled in the art shall ascertain.

A particularly suitable embodiment of the invention forms a mixedpercarboxylic acid composition by using more than one ester of apolyhydric alcohol and a C1 to C18 carboxylic acid as starting reagents.For example, in some embodiments, a mixed percarboxylic acid compositionincluding peracetic acid and peroctanoic acid is formed. To form thiscomposition, an ester of a polyhydric alcohol and a C1 carboxylic acidis combined with an ester of a polyhydric alcohol and a C8 carboxylicacid, a source of alkalinity, and an oxidizing agent. When forming amixed peracid composition, the order of addition can be varied dependingon the reaction conditions. For example, in some embodiments, all of thereagents can be combined and mixed in one step. Alternatively, in someembodiments, one of the esters can be added to a reaction vessel, withan oxidizing agent, and a source of alkalinity added sequentially. Thismixture can be allowed to react for an effective amount of time, priorto the second ester being added to the reaction mixture. Preparing themixed percarboxylic acid system in a stepwise manner also allows forcontrol of the reaction temperature. For example, by splitting theperhydrolysis reactions into two steps, the overall temperature of thereaction mixture is lower.

In some aspects of the invention, the order of addition and time forreaction can be varied according to the desired percarboxylic acidcomposition. That is, the reaction can be controlled so as to favor thereaction conditions for formation of each of the percarboxylic acidsindividually. For example, if it is known that one of the esters has akinetically slower perhydrolysis reaction rate, that ester can be addedto the reaction vessel first. After an amount of time sufficient tomaximize the percarboxylic acid formation of the first ester, the secondester with a kinetically faster perhydrolysis reaction rate can be addedto the reaction vessel.

According to additional aspects of the invention, the selected batchsize of a desired percarboxylic acid forming composition orpercarboxylic acid impacts the reaction kinetics. According to theinvention, a user- or system-inputted batch size (i.e. volume) to theABF system impacts the reaction kinetics. Although not intending to belimited to a particular theory, when generating various batch sizes withthe ABF system according to the invention, not all reactions arelinearly time-scaled, such that a larger batch size (i.e. hundreds ofgallons) may require a different timing sequence than a smaller batchsize (i.e. tens of gallons) depending on the reaction kinetics andvarious mixing parameters. The present invention accommodates thechanges in user- or system-inputted batch sizes, such that for differentvolumes of peracid compositions the time constants for its formulationwill vary.

In some aspects, the present disclosure provides methods for forming anantimicrobial and/or disinfecting composition. The methods includeproviding a mixed peroxycarboxylic acid forming composition. The mixedperoxycarboxylic acid forming composition includes: a first ester of apolyhydric alcohol and a C1 to C18 carboxylic acid, for example a C1 toC4 carboxylic acid; a second ester of a polyhydric alcohol and a C1 toC18 carboxylic acid, for example a C8 to C11 carboxylic acid; a sourceof alkalinity; and an oxidizing agent. After allowing the reactionmixture to react for a sufficient amount of time, a mixed percarboxylicacid composition is formed. The mixed peroxycarboxylic acid compositionis diluted with an acidic aqueous solution. In some embodiments, themixed peroxycarboxylic acid composition is diluted with an amount of anacidic aqueous solution effective to provide the diluted compositionwith a pH of about 1.0 to about 8.0.

In other aspects, the present disclosure provides methods for forming anantimicrobial and/or disinfecting composition including a singlepercarboxylic acid. The methods include providing a peroxycarboxylicacid forming composition. The composition includes: an ester of apolyhydric alcohol and a C1 to C18 carboxylic acid; a source ofalkalinity; and an oxidizing agent, wherein said composition has a pHgreater than 12. The peroxycarboxylic acid forming composition is thendiluted with an acidic aqueous solution. In some embodiments, thediluted acidic peroxycarboxylic acid composition has a pH of about 1.0to about 8.0.

Any acidic solution can be used to dilute the peroxycarboxylic acidcompositions. In an embodiment, the acidulant includes an inorganicacid. Suitable inorganic acids include, but are not limited to, sulfuricacid, sodium bisulfate, phosphoric acid, nitric acid, hydrochloric acid.In some embodiments, the acidulant includes an organic acid. Suitableorganic acids include, but are not limited to, methane sulfonic acid,ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid,xylene sulfonic acid, benzene sulfonic acid, formic acid, acetic acid,mono, di, or tri-halocarboyxlic acids, picolinic acid, dipicolinic acid,and mixtures thereof. In some embodiments, the compositions of thepresent invention are free or substantially free of a phosphorous basedacid.

Methods Employing Peracid Compositions

In some aspects, the present disclosure includes methods of using theperoxycarboxylic acid forming compositions disclosed herein. In someaspects, the methods of using the compositions employ a chemistry havinga pH of from about 0 to about 5 for various antimicrobial and/orbleaching applications. In other aspects, the methods of using thecompositions employ a chemistry having a pH of from about 5 to about 9for various antimicrobial and/or bleaching applications. In stillfurther aspects, the methods of using the compositions employ achemistry having a pH of from about 5 to about 14 for various bleachingapplications.

In some aspects, the present disclosure includes methods of using theperoxycarboxylic acid forming compositions and/or peroxycarboxylic acidsdisclosed herein. Peracid compositions generated according to theembodiments of the invention may be used for a variety ofuser-identified biocidal and/or anti-microbial purposes. In someaspects, the on-site generated peracid compositions may be employed forantimicrobial and/or bleaching methods of use. In further aspects, theon-site generated peracid compositions may be employed for anysanitizing methods of use. For example, the invention includes a methodfor reducing a microbial population, a method for reducing thepopulation of a microorganism on skin, a method for treating a diseaseof skin, a method for reducing an odor, or a method for bleaching. Thesemethods can operate on an object, surface, in a body or stream of wateror a gas, or the like, by contacting the object, surface, body, orstream with a peracid composition of the invention. Contacting caninclude any of numerous methods for applying a composition, such asspraying the composition, immersing the object in the composition, foamor gel treating the object with the composition, wiping the compositionor a combination thereof

In some aspects, a composition obtained according to the methods andapparatus of the present invention includes an amount of a peracidcomposition of the present invention effective for killing one or moreof the food-borne pathogenic bacteria associated with a food product,including, but not limited to, Salmonella typhimurium,Salmonellajaviana, Campylobacterjejuni, Listeria monocytogenes, andEscherichia coli O157:H7, yeast, and mold. In some embodiments, thecompositions obtained according to the methods and apparatus of thepresent invention include an amount of a peracid composition effectivefor killing one or more of the pathogenic bacteria associated with ahealth care surfaces and environments including, but not limited to,Salmonella typhimurium, Staphylococcus aureus, Salmonella choleraesurus,Pseudomonas aeruginosa, Escherichia coli, mycobacteria, yeast, and mold.The compositions obtained according to the methods and apparatus of thepresent invention have activity against a wide variety of microorganismssuch as Gram positive (for example, Listeria monocytogenes orStaphylococcus aureus) and Gram negative (for example, Escherichia colior Pseudomonas aeruginosa) bacteria, yeast, molds, bacterial spores,viruses, etc. The compositions obtained according to the methods andapparatus of the present invention, as described above, have activityagainst a wide variety of human pathogens. The present compositionsobtained according to the methods and apparatus of the present inventioncan kill a wide variety of microorganisms on a food processing surface,on the surface of a food product, in water used for washing orprocessing of food product, on a health care surface, in a health careenvironment or the like.

The compositions obtained according to the methods and apparatus of theinvention can be used for a variety of domestic or industrialapplications, e.g., to reduce microbial or viral populations on asurface or object or in a body or stream of water. The compositions canbe applied in a variety of areas including kitchens, bathrooms,factories, hospitals, dental offices, restaurants, clean in placeapplications, laundry or textile applications and food plants, and canbe applied to a variety of hard or soft surfaces having smooth,irregular or porous topography. Suitable hard surfaces include, forexample, architectural surfaces (e.g., floors, walls, windows, sinks,tables, counters and signs); eating utensils; hard-surface medical orsurgical instruments and devices; and hard-surface packaging. Such hardsurfaces can be made from a variety of materials including, for example,ceramic, metal, glass, wood or hard plastic.

Suitable soft surfaces include, for example, paper; filter media,hospital and surgical linens and garments; soft-surface medical orsurgical instruments and devices; and soft-surface packaging. Such softsurfaces can be made from a variety of materials including, for example,paper, fiber, woven or nonwoven fabric, soft plastics and elastomers.The compositions obtained according to the methods and apparatus of theinvention can also be applied to soft surfaces such as food and skin(e.g., a hand). The present compositions can be employed as a foaming ornonfoaming environmental sanitizer or disinfectant.

The peracid compositions obtained according to the methods and system ofthe present invention can be included in products such as sterilants,sanitizers, disinfectants, preservatives, deodorizers, antiseptics,fungicides, germicides, sporicides, virucides, detergents, bleaches,hard surface cleaners, hand soaps, waterless hand sanitizers, and pre-or post-surgical scrubs.

The compositions can also be used in veterinary products such asmammalian skin treatments or in products for sanitizing or disinfectinganimal enclosures, pens, watering stations, and veterinary treatmentareas such as inspection tables and operation rooms. The presentcompositions can be employed in an antimicrobial foot bath for livestockor people. The compositions can also be employed as an antimicrobialteat dip.

In some aspects, the compositions obtained according to the methods andapparatus of the present invention can be employed for reducing thepopulation of pathogenic microorganisms, such as pathogens of humans,animals, and the like. As one skilled in the art will ascertain, thereducing of pathogenic microorganism populations is particularlysuitable for healthcare and institutional applications of use. Thecompositions exhibit activity against pathogens including fungi, molds,bacteria, spores, and viruses, for example, S. aureus, E. coli,Streptococci, Legionella, Pseudomonas aeruginosa, mycobacteria,tuberculosis, phages, or the like. Such pathogens can cause a variety ofdiseases and disorders, including mastitis or other mammalian milkingdiseases, tuberculosis, and the like. The compositions of the presentinvention can reduce the population of microorganisms on skin or otherexternal or mucosal surfaces of an animal. In addition, the presentcompositions can kill pathogenic microorganisms that spread throughtransfer by water, air, or a surface substrate. The composition needonly be applied to the skin, other external or mucosal surfaces of ananimal water, air, or surface.

The peracid compositions obtained according to the methods and apparatusof the present invention can also be used on foods and plant species toreduce surface microbial populations; used at manufacturing orprocessing sites handling such foods and plant species; or used to treatprocess waters around such sites. For example, the compositions can beused on food transport lines (e.g., as belt sprays); boot and hand-washdip-pans; food storage facilities; anti-spoilage air circulationsystems; refrigeration and cooler equipment; beverage chillers andwarmers, blanchers, cutting boards, third sink areas, and meat chillersor scalding devices. The compositions of the invention can be used totreat produce transport waters such as those found in flumes, pipetransports, cutters, slicers, blanchers, retort systems, washers, andthe like. Particular foodstuffs that can be treated with compositions ofthe invention include, but are not limited to, eggs, meats, seeds,leaves, fruits and vegetables. Particular plant surfaces include bothharvested and growing leaves, roots, seeds, skins or shells, stems,stalks, tubers, corms, fruit, and the like. The compositions may also beused to treat animal carcasses to reduce both pathogenic andnon-pathogenic microbial levels.

The compositions can also be used to treat waste water where both itsantimicrobial function and its oxidant properties can be utilized. Asidefrom the microbial issues surrounding waste water, it is often rich inmalodorous compounds of reduced sulfur, nitrogen or phosphorous. Astrong oxidant such as the present invention converts these compoundsefficiently to their odor free derivatives e.g. the sulfates, phosphatesand amine oxides. These same properties are very useful in the pulp andpaper industry where the property of bleaching is also of great utility.

In some aspects, the compositions obtained according to the methods andapparatus of the present invention are useful in the cleaning orsanitizing of containers, processing facilities, or equipment in thefood service or food processing industries. The compositions haveparticular value for use on food packaging materials and equipment, andespecially for cold or hot aseptic packaging. Examples of processfacilities in which the composition of the invention can be employedinclude a milk line dairy, a continuous brewing system, food processinglines such as pumpable food systems and beverage lines, etc. Foodservice wares can be treated with an antimicrobial and/or disinfectedwith the composition of the invention. For example, the compositions canalso be used on or in ware wash machines, dishware, bottle washers,bottle chillers, warmers, third sink washers, cutting areas (e.g., waterknives, slicers, cutters and saws), egg washers or the like. Particulartreatable surfaces include, but are not limited to, packaging such ascartons, bottles, films and resins; dish ware such as glasses, plates,utensils, pots and pans; ware wash machines; exposed food preparationarea surfaces such as sinks, counters, tables, floors and walls;processing equipment such as tanks, vats, lines, pumps and hoses (e.g.,dairy processing equipment for processing milk, cheese, ice cream andother dairy products); and transportation vehicles. Containers includeglass bottles, PVC or polyolefin film sacks, cans, polyester, PEN or PETbottles of various volumes (100 ml to 2 liter, etc.), one gallon milkcontainers, paper board juice or milk containers, etc.

The compositions can also be used on or in other industrial equipmentand in other industrial process streams such as heaters, cooling towers,boilers, retort waters, rinse waters, aseptic packaging wash waters, andthe like. The compositions can be used to treat microbes and odors inrecreational waters such as in pools, spas, recreational flumes andwater slides, fountains, and the like. The composition can also be usedin treating microbes found in aqueous systems associated with petroleumor LP gas recovery or fermentation processes and pulp and paperprocesses and the like.

A filter containing peracid compositions of the present invention canreduce the population of microorganisms in air and liquids. Such afilter can remove water and air-born pathogens such as Legionella.

The compositions obtained according to the methods and apparatus of thepresent invention can be employed for reducing the population ofmicrobes, fruit flies, or other insect larva on a drain or othersurface.

The compositions of the present invention can also be employed bydipping food processing equipment into the use solution, soaking theequipment for a time sufficient to sanitize or destain the equipment,and wiping or draining excess solution off the equipment. Thecompositions of the present invention may be further employed byspraying or wiping food processing surfaces with the use solution,keeping the surfaces wet for a time sufficient to sanitize the surfaces,and removing excess solution by wiping, draining vertically, vacuuming,etc.

The compositions obtained according to the methods and system of thepresent invention may also be used in a method of sanitizing hardsurfaces such as institutional type equipment, utensils, dishes, healthcare equipment or tools, and other hard surfaces.

The compositions of the present invention can also be used for laundryor textile applications. The compositions can be employed by rinsinglaundry or textile surfaces with the use solution, keeping the surfaceswet for a sufficient time to wash, destain, sanitize, bleach and/orrinse the surface.

The peracid compositions can be applied to microbes or to soiled orcleaned surfaces using a variety of methods. These methods can operateon an object, surface, in a body or stream of water or a gas, or thelike, by contacting the object, surface, body, or stream with acomposition of the invention. Contacting can include any of numerousmethods for applying a composition, such as spraying the composition,immersing the object in the composition, rinsing the composition, foamor gel treating the object with the composition, applying with a wipesystem or a combination thereof.

A concentrate or use concentration of a peracid composition obtainedaccording to the methods and apparatus of the present invention can beapplied to or brought into contact with an object by any conventionalmethod or apparatus for applying an antimicrobial or cleaningcomposition to an object. For example, the object can be wiped with,sprayed with, foamed on, and/or immersed in the composition, or a usesolution made from the composition. The compositions can be sprayed,foamed, or wiped onto a surface; the composition can be caused to flowover the surface, or the surface can be dipped into the composition.Contacting can be manual or by machine. Food processing surfaces, foodproducts, food processing or transport waters, and the like can betreated with liquid, foam, gel, aerosol, gas, wax, solid, or powderedperacid compositions according to the invention, or solutions containingthese compositions.

Other hard surface cleaning applications for the compositions includeclean-in-place systems (CIP), clean-out-of-place systems (COP),washer-decontaminators, sterilizers, textile laundry machines, ultra andnano-filtration systems and indoor air filters. COP systems can includereadily accessible systems including wash tanks, soaking vessels, mopbuckets, holding tanks, scrub sinks, vehicle parts washers,non-continuous batch washers and systems, and the like. CIP systemsinclude the internal components of tanks, lines, pumps and other processequipment used for processing typically liquid product streams such asbeverages, milk, juices.

A method of sanitizing substantially fixed in-place process facilitiesincludes the following steps. A composition in accordance with variousembodiments of the invention is introduced into the process facilitiesat a temperature in the range of about 4° C. to 60° C. Afterintroduction of the composition, the solution is held in a container orcirculated throughout the system for a time sufficient to sanitize theprocess facilities (e.g., to kill undesirable microorganisms). After thesurfaces have been sanitized by means of the present compositions, thesolution is drained. Upon completion of the sanitizing step, the systemoptionally may be rinsed with other materials such as potable water. Thecompositions can be circulated through the process facilities for 10minutes or less.

The present methods can include delivering the present composition viaair delivery to the clean-in-place or other surfaces such as thoseinside pipes and tanks. This method of air delivery can reduce thevolume of solution required.

Methods for Contacting a Food Product

In some aspects, the present invention provides methods for contacting afood product with compositions according to the invention employing anymethod or apparatus suitable for applying such compositions. Forexample, in some embodiments, the food product is contacted by thecompositions with a spray of the compositions, by immersion in thecompositions, by foam or gel treating with the compositions. Contactwith a spray, a foam, a gel, or by immersion can be accomplished by avariety of methods known to those of skill in the art for applyingantimicrobial agents to food. Contacting the food product can occur inany location in which the food product might be found, such as field,processing site or plant, vehicle, warehouse, store, restaurant, orhome. These same methods can also be adapted to apply the compositionsof the present invention to other objects.

The present methods require a certain minimal contact time of thecompositions with food product for occurrence of significantantimicrobial effect. The contact time can vary with concentration ofthe use compositions, method of applying the use compositions,temperature of the use compositions, amount of soil on the food product,number of microorganisms on the food product, type of antimicrobialagent, or the like. The exposure time can be at least about 5 to about15 seconds. In some embodiments, the exposure time is about 15 to about30 seconds. In other embodiments, the exposure time is at least about 30seconds.

In some embodiments, the method for washing a food product employs apressure spray including compositions of the present invention. Duringapplication of the spray solution on the food product, the surface ofthe food product can be moved with mechanical action, e.g., agitated,rubbed, brushed, etc. Agitation can be by physical scrubbing of the foodproduct, through the action of the spray solution under pressure,through sonication, or by other methods. Agitation increases theefficacy of the spray solution in killing micro-organisms, perhaps dueto better exposure of the solution into the crevasses or small coloniescontaining the micro-organisms. The spray solution, before application,can also be heated to a temperature of about 15 to 20° C., for example,about 20 to 60° C. to increase efficacy. The spray stabilizedcompositions can be left on the food product for a sufficient amount oftime to suitably reduce the population of microorganisms, and thenrinsed, drained, or evaporated off the food product.

Application of the material by spray can be accomplished using a manualspray wand application, an automatic spray of food product moving alonga production line using multiple spray heads to ensure complete contact,or other spray apparatus. One automatic spray application involves theuse of a spray booth. The spray booth substantially confines the sprayedcompositions to within the booth. The production line moves the foodproduct through the entryway into the spray booth in which the foodproduct is sprayed on all its exterior surfaces with sprays within thebooth. After a complete coverage of the material and drainage of thematerial from the food product within the booth, the food product canthen exit the booth. The spray booth can include steam jets that can beused to apply the stabilized compounds of the invention. These steamjets can be used in combination with cooling water to ensure that thetreatment reaching the food product surface is less than 65° C., e.g.,less than 60° C. The temperature of the spray on the food product isimportant to ensure that the food product is not substantially altered(cooked) by the temperature of the spray. The spray pattern can bevirtually any useful spray pattern.

Immersing a food product in the liquid compositions of the presentinvention can be accomplished by any of a variety of methods known tothose of skill in the art. For example, the food product can be placedinto a tank or bath containing the compositions. Alternatively, the foodproduct can be transported or processed in a flume of the compositions.The washing solution can be agitated to increase the efficacy of thesolution and the speed at which the solution reduces micro-organismsaccompanying the food product. Agitation can be obtained by conventionalmethods, including ultrasonics, aeration by bubbling air through thesolution, by mechanical methods, such as strainers, paddles, brushes,pump driven liquid jets, or by combinations of these methods. Thewashing solution can be heated to increase the efficacy of the solutionin killing micro-organisms. After the food product has been immersed fora time sufficient for the desired antimicrobial effect, the food productcan be removed from the bath or flume and the compositions can berinsed, drained, or evaporated off the food product.

In other embodiments, a food product can be treated with a foamingversion of the compositions of the present invention. The foam can beprepared by mixing foaming surfactants with the washing solution at timeof use. The foaming surfactants can be nonionic, anionic or cationic innature. Examples of useful surfactant types include, but are not limitedto the following: alcohol ethoxylates, alcohol ethoxylate carboxylate,amine oxides, alkyl sulfates, alkyl ether sulfate, sulfonates,including, for example, alkyl aryl sulfonates, quaternary ammoniumcompounds, alkyl sarcosines, betaines and alkyl amides. The foamingsurfactant is typically mixed at time of use with the washing solution.Use solution levels of the foaming agents is from about 50 ppm to about2.0 wt-%. At time of use, compressed air can be injected into themixture, then applied to the food product surface through a foamapplication device such as a tank foamer or an aspirated wall mountedfoamer.

In some embodiments, a food product can be treated with a thickened orgelled version of the compositions of the present invention. In thethickened or gelled state the washing solution remains in contact withthe food product surface for longer periods of time, thus increasing theantimicrobial efficacy. The thickened or gelled solution will alsoadhere to vertical surfaces. The compositions can be thickened or gelledusing existing technologies such as: xanthan gum, polymeric thickeners,cellulose thickeners, or the like. Rod micelle forming systems such asamine oxides and anionic counter ions could also be used. The thickenersor gel forming agents can be used either in the concentrated product ormixing with the washing solution, at time of use. Typical use levels ofthickeners or gel agents range from about 100 ppm to about 10 wt-%.

Methods for Beverage, Food, and Pharmaceutical Processing

The compositions of the present invention can be used in the manufactureof beverage, food, and pharmaceutical materials including fruit juice,dairy products, malt beverages, soybean-based products, yogurts, babyfoods, bottled water products, teas, cough medicines, drugs, and softdrinks. The compositions of the present invention can be used tosanitize, disinfect, act as a sporicide for, or sterilize bottles,pumps, lines, tanks and mixing equipment used in the manufacture of suchbeverages. Further, the compositions of the present invention can beused in aseptic, cold filling operations in which the interior of thefood, beverage, or pharmaceutical container is sanitized or sterilizedprior to filling. In such operations, a container can be contacted withthe compositions, typically using a spray, dipping, or filling device tointimately contact the inside of the container with the compositions,for a sufficient period of time to reduce microorganism populationswithin the container. The container can then be emptied of the amount ofsanitizer or sterilant used. After emptying, the container can be rinsedwith potable water or sterilized water and again emptied. After rinsing,the container can be filled with the beverage, food, or pharmaceutical.The container can then be sealed, capped or closed and then packed forshipment for ultimate sale. The sealed container can be autoclaved orretorted for added microorganism kill.

In food, beverage, or pharmaceutical manufacturing, fungalmicroorganisms of the genus Chaetomium or Arthrinium, and spores orbacteria of the genus Bacillus spp. can be a significant problem inbottling processes, particularly in cold aseptic bottling processes. Thecompositions of the present invention can be used for the purpose ofcontrolling or substantially reducing (by more than a 5 log₁₀ reduction)the number of Chaetomium or Arthrinium or Bacillus microorganisms inbeverage or food or pharmaceutical bottling lines using cold asepticbottling techniques.

In such techniques, metallic, aluminum or steel cans can be filled,glass bottles or containers can be filled, or plastic (PET or PBT orPEN) bottles, and the like can be filled using cold aseptic fillingtechniques. In such processes, the compositions of the invention can beused to sanitize the interior of beverage containers prior to fillingwith the carbonated (or noncarbonated) beverage. Typical carbonatedbeverages in this application include, but are not limited to, colabeverages, fruit beverages, ginger ale beverages, root beer beverages,iced tea beverages which may be non-carbonated, and other commonbeverages considered soft drinks. The compositions of the invention canbe used to sanitize both the tanks, lines, pumps, and other equipmentused for the manufacture and storage of the soft drink material and alsoused in the bottling or containers for the beverages. In an embodiment,the compositions are useful for killing both bacterial and fungalmicroorganisms that can be present on the surfaces of the productionequipment and beverage containers.

Methods for Industrial Processing

In some aspects, the invention includes methods of using theperoxycarboxylic acid forming compositions and/or peroxycarboxylic acidsto prevent biological fouling in various industrial processes andindustries, including oil and gas operations, to control microorganismgrowth, eliminate microbial contamination, limit or prevent biologicalfouling in liquid systems, process waters or on the surfaces ofequipment that come in contact with such liquid systems. As referred toherein, microbial contamination can occur in various industrial liquidsystems including, but not limited to, air-borne contamination, watermake-up, process leaks and improperly cleaned equipment. In anotheraspect, the peroxycarboxylic acid forming compositions and/orperoxycarboxylic acids are used to control the growth of microorganismsin water used in various oil and gas operations. In a further aspect,the compositions are suitable for incorporating into fracturing fluidsto control or eliminate microorganisms.

For the various industrial processes disclosed herein, “liquid system”refers to flood waters or an environment within at least one artificialartifact, containing a substantial amount of liquid that is capable ofundergoing biological fouling, it includes but is not limited toindustrial liquid systems, industrial water systems, liquid processstreams, industrial liquid process streams, industrial process watersystems, process water applications, process waters, utility waters,water used in manufacturing, water used in industrial services, aqueousliquid streams, liquid streams containing two or more liquid phases, andany combination thereof.

In at least one embodiment this technology would be applicable to anyprocess or utility liquid system where microorganisms are known to growand are an issue, and biocides are added. Examples of some industrialprocess water systems where the method of this invention could beapplied are in process water applications (flume water, shower water,washers, thermal processing waters, brewing, fermentation, CIP (clean inplace), hard surface sanitization, etc.), Ethanol/Bio-fuels processwaters, pretreatment and utility waters (membrane systems, ion-exchangebeds), water used in the process/manufacture of paper, ceiling tiles,fiber board, microelectronics, E-coat or electro depositionapplications, process cleaning, oil exploration and energy services(completion and work over fluids, drilling additive fluids, fracturingfluids, flood waters, etc.; oil fields—oil and gas wells/flow line,water systems, gas systems, etc.), and in particular water systems wherethe installed process equipment exhibits lowered compatibility tohalogenated biocides.

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, numerous equivalents to thespecific procedures, embodiments, claims, and examples described herein.Such equivalents are considered to be within the scope of this inventionand covered by the claims appended hereto. The contents of allreferences, patents, and patent applications cited throughout thisapplication are hereby incorporated by reference. The invention isfurther illustrated by the following examples, which should not beconstrued as further limiting.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated by reference.

EXAMPLES

Embodiments of the present invention are further defined in thefollowing non-limiting Examples. It should be understood that theseExamples, while indicating certain embodiments of the invention, aregiven by way of illustration only. From the above discussion and theseExamples, one skilled in the art can ascertain the essentialcharacteristics of this invention, and without departing from the spiritand scope thereof, can make various changes and modifications of theembodiments of the invention to adapt it to various usages andconditions. Thus, various modifications of the embodiments of theinvention, in addition to those shown and described herein, will beapparent to those skilled in the art from the foregoing description.Such modifications are also intended to fall within the scope of theappended claims.

Equipment configuration and software were developed for on-sitegeneration of peracid compositions, including peroxycarboxylic acidforming compositions and peroxycarboxylic acid for use as biocides. Areactor module meeting the hydraulic requirements of the reactionkinetics was developed to obtain precise and repeatable generation ofactive peracid chemistry. In addition, a software algorithm wasdeveloped to run one or multiple reactor modules to sequence eventsappropriately to maximize active yield and safely operate the reactormodule.

Example 1

An exemplary single reaction vessel adjustable biocide formulator orgenerator system is configured according to FIG. 2. In the singlereactor model, peroxyoctanoic acid and peroxyacetic acid were generatedthrough the addition of the sugar esters sorbitol octanoate andtriacetin, respectively. The sugar esters were added at different timesto coordinate the completion of the hydrolysis reactions. In the singlereactor model the sugar esters are reacted in a single vessels, suchthat the sugars are added according to reaction kinetics. For mixedperacid systems, an exemplary multiple reaction vessel ABF configuredaccording to FIG. 3 or 4 was used such that a second reactor module maybe run in parallel.

The control software calculates the dosage and mix time and delay pumpsequencing so that both reactions to generate intermediates arecompleted at the same time. Intermediates may be pumped to a third mixmodule before pumping to a sump reservoir or dosing into the cleaningprocess.

For both single and/or mixed peracid systems, raw material feed timesvary according to the desired peracid system selected by a user orsystem controller input. Raw materials may be dosed at the same time, inparallel to more than one reaction vessel and/or sequentially to one ormore reaction vessels of the ABF system. Understanding when theperhydrolysis reaction starts is key to calculating reaction time. Forexample; the reaction time starts when the pH of the reaction mixture isincreased through the addition of the caustic into the vessel and notwhen caustic addition is finished. It is therefore advantageous to dosethe caustic to the reaction vessel as quickly as possible.

Example 2

Adjustable biocide formulator system operating procedures. A user orprocess controller input determines the desired peracid formulation andvolume to be generated on-site. Input information is loaded into theformulator system. Formulator software calculates the time required todose raw materials into reactor(s) and reaction time.

Upon set up, feed pumps are calibrated. Raw materials are fed toreaction vessel(s) and mixed in reaction vessel for a period of time forperhydrolysis reaction to take place. The extent of reaction is measuredto determine when to quench a reaction with acid. Acid is either dosedinto a reaction vessel at end of a mix period for short lifeintermediates or is dosed at a later time for longer lastingintermediates. The intermediates are pumped to a sump reservoir fordosing to a cleaning process or are dosed directly from reaction vesselinto a cleaning process.

Example 3

Titrations of ABF Perhydrolysis Reactions

Duplicates Vol Titrant Vol Titrant POOA Peracid H₂O₂ Total Av. ConsumedConsumed Mol. Mol. Wt of Normality Sample Peracid meas'd meas'd O₂ EP1EP2 Wt of Wt of Sample of Thio volume Type (% w/w) (wt %) (w/w&) (mL)(mL) Peracid H₂O₂ (g) (N) (mL) POOA 1.07 1.55 0.84 6.73 52.47 160 346.610 0.100 0.100 ABF 0832 1.09 1.58 0.85 6.23 48.69 160 34 6.000 0.1000.100 pH 5.07 1.08 1.57 0.84 POOA 1.33 1.88 1.02 4.08 31.27 160 34 3.2400.100 0.100 ABF 1035 1.34 1.87 1.01 4.05 30.62 160 34 3.180 0.100 0.100pH 4.92 1.33 1.87 1.01 POOA 1.26 1.85 1.00 3.90 31.00 160 34 3.270 0.1000.100 ABF 1103 1.05 1.56 0.84 3.80 30.31 160 34 3.800 0.100 0.100 pH4.96 1.15 1.71 0.92 Sample POOA % 0832 1.09 1035 1.34 1103 1.05 13251.10 1351 1.10 Ave 1.14 Stdev 0.12 RSD 10% *Samples were quenched with 6mL of AcOH-100 per 100 mL of fresh perhydrolysis/reaction solution.After AcOH quenching they were further diluted by the addition of 26 gof NAS-Fal/106 g of the above solution to homogenous the two phasesquenched solutions. Therefore every reaction solution was diluted to 76%of its original activity and this was therefore built back into thecalculations above thus the values displayed are the actual activitiesof the reaction solutions.

Example 4

A study was performed to evaluate the ability to generate a mixedperoxycarboxylic acid composition in situ from ester starting materialsat alkaline pHs. For this study, 1.28 grams of sorbitan octanoate, 14.68grams of water, and 3.66 grams of a 35% hydrogen peroxide solution wereadded in a 100 mL beaker. With magnetic stirring, 14.64 grams of a 10%sodium hydroxide solution was added to the beaker. The solution wasmixed for ten minutes. Then, 1.70 grams of triacetin was added to thesolution. After mixing for an additional five minutes, the solution wassampled to measure the peroxyacetic (POAA) and peroxyoctanoic (POOA)acid concentrations.

This two step addition process was also compared to a one step process.For the one step process, 1.26 grams of sorbitan octanoate, 1.70 gramsof triacetin, 14.67 grams of water, and 3.66 grams of a 35% hydrogenperoxide solution were added in a 100 mL beaker. With magnetic stirring,14.64 grams of a 10% sodium hydroxide solution was added to the beaker.After mixing for 15 minutes, the solution was sampled for POAA and POOAlevels. The results for both the two step and the one step reactionmethods are shown in the table below.

TABLE 1 Peroxyacetic/ Peroxy- Peroxy- Peroxy- ocatanoic Temper- aceticoctanoic (wt % as ature pH Reaction Acid Acid Peroxyacetic (maxi-(initial- Process (wt %) (wt %) acid) mum) end) Two Step 4.32 0.71 4.8924.6° C. 12.19-11.47 One Step 3.95 0.60 4.33 28.1° C. 11.75-11.60

As can be seen from this table, the two step process delivered higherlevels of POOA and POAA. It was also found that using the two stepprocess described above generated lower temperatures than the one stepprocess. These lower temperatures are important from both a safety and astability standpoint for this reaction. Without wishing to be bound byany particular theory, it is thought that in the two step process, thekinetically slower perhydrolysis reaction of sorbitan octanoate wasexposed to a more favorable perhydrolysis condition than in the one stepreaction. That is in the two step process, the sorbitan octanoate isexposed to a higher pH and stoichiometrically more hydrogen peroxide. Itis thought that these conditions contributed to the higher yield ofPOOA. Further, it is thought that the kinetically fast perhydrolysisreaction of triacetin was given enough perhydrolysis reaction time, butavoided a prolonged exposure to a high pH condition, and thus achieved abetter POAA yield.

Example 5

Rheology of sugar esters. Rheology modifiers may optionally be includedin the methods according to the present invention. Water soluble orwater dispersible rheology modifiers that are useful can be classifiedas inorganic or organic. The organic thickeners can further be dividedinto natural and synthetic polymers with the latter still furthersubdivided into synthetic natural-based and synthetic petroleum-based.

Additional experimentation demonstrates the best rheology of the esterto increase accuracy.

Example 6

A series of experiments were conducted to determine the impact of theorder of addition of reagents on the generation of peracid chemistryusing the ABF generator according to the invention. The ABF generatoraccording to the invention has demonstrate efficacy in the production ofa peroxyoctanoic acid solutions though combination of precursorchemistries (e.g. ester premix with hydroxide and/or other activators)combined prior to having the reactants enter a reaction vessel.Surprisingly, an aspect of the invention involves the impact of reagentaddition order and dilution of the reagents on the generation of peracidchemistry. Aspects of the invention disclose preferred operating methodsfor generating a consist output (which is non-fouling) from the mixerand reaction vessel.

First, the ABF generator mixed reagents in the following order anddesign: water, ester/peroxide, NaOH to form peracid. In particular, whenthe system was activated it injected water, ester/peroxide premix, and50% caustic into a series of clear PVC injection manifolds that wereplumbed together in series. The flow rate for all reagents entering thesystem was controlled at 25 g/min. Samples of the resultant mixture werecollected at the exit of the solution and were titrated using aniodometric titration procedure for peroxyoctanoic acid 10 minutes afterthe reagents were initially mixed. The resultant titration yielded aperacid concentration of approximately 1.75%. Based on the reagentformulation a POOA concentration of approximately 5.50% was expected.Upon evaluation of the mixing manifold it was apparent that a waxy solidwas formed between the ester and NaOH injection ports, providing arationale for the low POOA titration. In particular, a poor masstransfer through the system resulted from the mix order of the reagents.

The second test order of ABF generator mixed reagents occurred nearlythe same as the first example, with the exception that the injectionpoints for the ester/peroxide premix and the NaOH were reversed. Inparticular, when the system was activated it injected water, 50% causticand an ester/peroxide premix into a series of clear PVC injectionmanifolds that were plumbed together in series. The results were thesame as those outlined in the first example run of this Experiment 6,showing that under concentration conditions mixing order alone cannotovercome the fouling of the reagents.

The third example, tested the theory that the formation of the solid wasa reaction between the concentrated ester and concentrated caustic. Thiswas tested by combining 5 grams of glycerol octanoate with 5 grams of50% NaOH in a 150 ml beaker. When the 2 materials were mixed theyimmediately formed a waxy solid that was very difficult to dissolve evenin hot, approximately about 60° C. (140° F.) water. This test confirmedthe importance of dilute the caustic and/or sugar ester premix prior toreaction within the systems according to the invention.

A fourth test was conducted based on the results of the prior testswithin this Example 6 to confirm whether an issue with the formation ofthe solid (e.g. fouled reagents) was poor dispersion of theester/peroxide premix in the water prior to addition of the caustic. Toalleviate this issue an injection manifold was re-designed to pre-mixthe ester/peroxide solution with water prior to addition of the NaOH. Inparticular, an ester/peroxide premix is diluted and mixed within astatic mixer prior to the addition of the caustic. Unexpectedly, thepremixing of the ester/peroxide and water did not alleviate theprecipitation issue (e.g. fouling of the reagents) as a precipitatestill formed downstream from the addition of the NaOH. In addition, whentitrating the solution a peracid concentration of POOA less than 1.0%was measured.

A fifth test was conducted. The order of addition of the reagents wasfurther modified. In particular, the ester/peroxide premix and NaOHpremix injection ports on the injection manifold were switched. Inparticular, when the system was activated it injected water and 50%caustic, prior to the addition of the ester/peroxide premix into thesystem. The outcome of this change in mix order of reagents was expectedto generate similar or even poorer results relative to those from priorexamples as this mixing profile would produce even less dispersion ofester/peroxide. Surprisingly, changing the order of addition had amarked effect on the reaction. Mixing the components in this mannerproduced a uniform output from the mixing manifold with noprecipitation. In addition a sample of the peracid chemistry produced bythis modified mixing system titrated a 5.46% peroxyoctanoic acid yieldat 10 minutes after the chemistry precursors were combined.

The tests and results demonstrate the importance of the order ofaddition (e.g. diluted caustic followed by ester/peroxide premix).

Example 7

A series of experiments were conducted to determine the impact ofreagent concentration on the generation of peracid chemistry using theABF generator according to the invention. In particular, the level ofNaOH dilution to ensure uniform dispersion of the ester component wasfurther analyzed. As set forth in Table 2, 5 grams of a sugar ester wereadded to 5 grams of NaOH at varying concentrations—50%, 25%, 20%, 15%,12.5% and 6.25%. The reagents were added in test tubes with mildagitation. Production of precipitate in this test is an indication thatthe NaOH dilution is insufficient to produce a uniform output from thissystem.

TABLE 2 NaOH oncentration 50% 25% 20% 15% 12.5% 6.25% Ester/ White WhiteWhite White Turbid Turbid NaOH Solid Solid solid solid single single Rxnrapidly rapidly phase phase dissolves dissolves and and dispersesdisperses to a single to a single phase phase

The results shown in Table 2 demonstrate that the adjustable biocideformulator or generator system should deliver a NaOH solution that is nomore than 20 wt-% on an actives basis before the ester component iscombined with the NaOH to initiate the peracid production reaction.

The inventions being thus described, it will be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the inventions and all suchmodifications are intended to be included within the scope of thefollowing claims.

The invention claimed is:
 1. An adjustable biocide formulator orgenerator system for on-site peroxycarboxylic acid forming compositiongeneration comprising: an apparatus comprising at least one reactionvessel, a series of feed pumps and an outlet for dosing aperoxycarboxylic acid forming composition from said reaction vessel;wherein said feed pumps are in fluid connection with said reactionvessel and supply reagents to produce said peroxycarboxylic acid formingcomposition in said reaction vessel; wherein said reagents comprise anester of a polyhydric alcohol and a C1 to C18 carboxylic acid, a sourceof alkalinity, an acid or acidic aqueous solution, and an oxidizingagent; wherein said reaction vessel is in fluid connection with saidoutlet to dispense said peroxycarboxylic acid forming composition; andwherein said peroxycarboxylic acid forming composition is an individualor mixed peroxycarboxylic acid forming composition according to a user-or system-inputted selection.
 2. The system according to claim 1,wherein the source of alkalinity is sodium hydroxide, and wherein saidsodium hydroxide is provided to said reaction vessel prior to theaddition of said ester in a solution that is less than about 20 wt-%sodium hydroxide on an actives basis.
 3. The system according to claim1, further comprising at least one measurement device, wherein saidmeasurement device measures one or more reaction kinetics or systemoperations for said peroxycarboxylic acid forming composition generationselected from the group consisting of fluorescence, weight, flow,capacitive level, pH, oxidation reduction potential, pressure,temperature and combinations thereof.
 4. The system according to claim1, wherein said ester and other reagents are fed sequentially to saidreaction vessel to produce a single peroxycarboxylic acid formingcomposition, and wherein said ester is selected from the groupconsisting of monooctanoic glyceride, dioctanoic glyceride, trioctaonoicglyceride, sorbitan monooctanoate, sorbitan dioctanoate, sorbitantrioctanoate, laurate sucroside and mixtures and derivatives thereof. 5.The system according to claim 1, wherein more than one ester is addedwith said other reagents to a single reaction vessel or separatereaction vessels sequentially or in parallel to produce a mixedperoxycarboxylic acid forming composition, wherein said ester isselected from the group consisting of monooctanoic glyceride, dioctanoicglyceride, trioctaonoic glyceride, sorbitan monooctanoate, sorbitandioctanoate, sorbitan trioctanoate, laurate sucroside and mixtures andderivatives thereof.
 6. The system according to claim 1, wherein saidapparatus further comprises a reservoir in fluid connection with saidreaction vessel outlet to mix or store said peroxycarboxylic acidforming compositions from said reaction vessel, and/or an additionalfeed pump providing the acid or acidic aqueous solution in fluidcommunication with said reaction vessel or said reservoir, wherein saidacid or acidic aqueous solution dilutes said peroxycarboxylic acidforming composition to form a peroxycarboxylic acid having a pH of about1.0 to about 8.0, and/or at least one component selected from the groupconsisting of additional mixers, circulation pumps, holding vessels,reagent delivery sensors or combinations of the same.
 7. The systemaccording to claim 1, further comprising a control software foroperating said apparatus to generate a user- or system-inputtedperoxycarboxylic acid forming composition and desired volume of saidperoxycarboxylic acid forming composition for on-site generation,wherein said control software determines the timing of feeding said rawmaterials to said reaction vessel, mixing and reaction time required forproduction of said user- or system-inputted peroxycarboxylic acidforming composition and desired volume.
 8. The system according to claim1, wherein said ester is traicetin or sorbitan octanoate, wherein saidoxidizing agent comprises a hydrogen peroxide donor, and wherein saidthe source of alkalinity is selected from the group consisting of analkaline metal hydroxide, an alkaline earth metal hydroxide, an alkalimetal silicate, an alkali metal carbonate, borates and mixtures thereof.9. The system according to claim 1, further comprising a data outputmeans for sharing information related to said peroxycarboxylic acidforming composition formulation, peroxycarboxylic acid formingcomposition consumption or usage, additional peroxycarboxylic acidforming composition production-related data or combinations of the same.10. A method for on-site peroxycarboxylic acid forming compositiongeneration or peroxycarboxylic acid generation comprising: inputting auser- or system-controlled peroxycarboxylic acid forming composition orperoxycarboxylic acid formulation into a control software for anadjustable biocide formulator or generator system, wherein said inputformulation selects an individual or mixed peroxycarboxylic acid formingcomposition or peroxycarboxylic acid and corresponding volume or massfor on-site generation; and mixing one or more sugar esters of apolyhydric alcohol and a C1 to C18 carboxylic acid, a source ofalkalinity, an acid or acidic aqueous solution, and an oxidizing agentat alkaline pH in the adjustable biocide formulator or generator systemof claim 1 at a pH above at least
 12. 11. The method according to claim10, wherein the source of alkalinity is sodium hydroxide, and whereinsaid sodium hydroxide is provided to said reaction vessel prior to theaddition of said ester and said acid or acidic aqueous solution in asolution that is less than about 20 wt-% sodium hydroxide on an activesbasis.
 12. The method according to claim 11, wherein said sodiumhydroxide is diluted with water to the target concentration of less thanabout 20 wt-% within the system and prior to the addition of said ester.13. The method according to claim 10, wherein said input is a user or asystem selecting a peroxycarboxylic acid or peroxycarboxylic acidforming composition, wherein said system is selected from the groupconsisting of a CIP process, bottle washer, aseptic filler, vegetablewash or rinse sink, 3^(rd) sink sanitizing sink, textile bleachingprocess and combinations thereof.
 14. The method according to claim 13,wherein said user or a system input further selects a single or multiplereaction vessel mode for peroxycarboxylic acid and/or mixedperoxycarboxylic acid or peroxycarboxylic acid forming compositiongeneration.
 15. The method according to claim 14 further comprisingtiming the addition of said esters in parallel or sequentially forreaction in a single reaction vessel or separate reaction vessels, andcombining peroxycarboxylic acid forming compositions from separatereaction vessels into an additional reaction vessel or a reservoir. 16.The method according to claim 10, further comprising measuring theextent of said ester perhydrolysis reaction using one or moremeasurement devices, wherein said measurement device measures one ormore reaction kinetics or system operations for said peroxycarboxylicacid generation selected from the group consisting of fluorescence,weight, flow, capacitive level, pH, oxidation reduction potential,pressure, temperature and combinations thereof.
 17. The method accordingto claim 16, wherein said measurement devices determine when to dilutesaid peroxycarboxylic acid forming composition with the acid or aqueousacidic solution to form said peroxycarboxylic acid.
 18. The methodaccording to claim 10, further comprising providing the acid or aqueousacidic solution to form a peroxycarboxylic acid having a pH of about 1.0to about 8.0.
 19. The method according to claim 10, further comprisingdispensing said peroxycarboxylic acid forming composition for use in acleaning process, and wherein said mixing step takes place in saidreaction vessel using a mechanical blade mixer having a variable speedcontrol motor to achieve homogeneous blending of reagents.
 20. A methodof cleaning using an on-site generated peroxycarboxylic acid formingcomposition comprising: obtaining a user- or system-inputtedperoxycarboxylic acid forming composition on-site using the adjustablebiocide formulator or generator system of claim 1; applying saidperoxycarboxylic acid forming composition in an amount sufficient tosanitize, bleach and/or disinfect a surface in need thereof.